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mm 


TREATISE 

ON  THE 

COLORING  MATTERS  DERIVED  FROM  COAL  TAR.  - 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/treatiseoncoloriOOduss_0 


TREATISE 


ON  THE 


COLORING  MATTERS  DERIVED  FROM 
COAL  TAR; 

THEIK 

Ipratfeal  giplicatixm  in  ggnng  Cotton,  Wool,  aub  Silk. 


THE 

PRINCIPLES  OF  THE  ART  OF  DYEING  AND  THE  DISTILLATION 
OF  COAL  TAR, 

WITH  A  DESCRIPTION  OF  THE 
| 

MOST  IMPORTANT  NEW  DYES  NOW  IN  USE. 


BY 

Professor  H.  DTJSSAUCE,  Chemist, 

Lately  of  the  Laboratories  of  the  French  Government,  viz.,  the  Mining 
Botanical  Garden,  the  Imperial  Manufacture  of  the  Gobelins,  the 
Conservatoire  Imperiale  of  Arts  and  Manufactures,  Professor 
of  Industrial  Chemistry  to  the  Polytechnic  Institute, 
Paris. 


PHILADELPHIA : 

HENRY  CAREY  BAIRD, 
INDUSTRIAL  PUBLISHER, 
406  Walnut  Street. 

1863. 


Entered  according  to  Act  of  Congress,  in  the  year  1863,  by 

HENRY  CAREY  BAIRD, 

in  the  Clerk's  Office  of  the  District  Court  of  the  United  States  in 
and  for  the  Eastern  District  of  Pennsylvania. 


PHILADELPHIA  : 
COLLINS,  PRINTER. 


THE  GETTY  CENTER 
LIBRARY 


PREFACE. 


The  object  of  this  work  is  not  to  present 
to  the  public  a  treatise  on  the  art  of  dyeing, 
but  simply  to  furnish  a  full  and  clear  de- 
scription of  those  colors  concerning  which 
so  much  is  said  and  so  little  known. 

The  greater  part  of  the  coloring  matters 
employed  by  dyers,  belongs  to  the  vegetable, 
a  few  to  the  mineral,  and  fewer  still  to  the 
animal  kingdoms.  Within  a  few  years  past 
a  great  variety  of  colors,  among  which  are 
crimson,  red,  violet,  blue,  green,  scarlet  and 
yellow,  have  been  obtained  from  a  single  sub- 
stance— coal  tar — and  the  shades  produced 
on  silk  and  wool  by  these  colors  are  unri- 
valled in  beauty. 

As  yet  no  distinct  treatise  on  this  subject 
has  been  published ;  all  the  information  we 

P 


37  7  / 


Vi 


PREFACE. 


have  is  found  scattered  here  and  there 
through  many  scientific  and  industrial  publi- 
cations, and  thus  rendered  almost  inaccessible 
to  the  practitioner.  Our  object  has  been  to 
collect  these  scattered  items,  and,  in  con- 
nection with  our  knowledge  of  the  subject, 
prepare  a  practical  work  for  the  dyer  and 
calico  printer,  authors  having  devoted  them- 
selves more  to  the  theory  than  the  practice. 
The  manipulations  described  in  the  different 
journals  are  difficult,  and  the  great  number  of 
formula)  used,  render  the  explanation  unin- 
telligible to  any  one  not  acquainted  with 
chemical  theories.  We  have  endeavored  to  so 
simplify  the  recipes  and  minutely  describe  the 
manipulations  as  to  enable  any  one,  though 
not  a  chemist,  to  manufacture  these  colors. 
The  principal  works  which  we  have  consulted 
are :  Les  Comptes  Rendus,  Annates  de  Chimie 
et  de  Physique,  Bulletin  de  la  Societe  d^ encou- 
ragement^ Moniteur  industries  The  Chemical 
News,  London  Journal  of  Pharmacy,  Ameri- 
can Druggists  Circular,  etc.  etc. 


PREFACE. 


vii 


The  book  is  divided  into  several  chapters. 
The  first  is  devoted  to  the  general  notions  of 
the  art  of  dyeing;  several  treat  of  the  fabri- 
cation of  colors  of  coal  tar  and  their  applica- 
tions ;  and  we  terminate  by  the  processes  to 
manufacture  different  new  colors,  and  the 
theory  of  the  fixation  of  colors  and  mordants. 

This  work,  the  only  one  of  the  kind  thus 
far  published,  we  trust  is  destined  to  render 
great  services  to  the  dyer  by  removing  the 
uncertainties  now  attending  this  new  branch 
of  industry,  and  enabling  the  dyer  himself 
to  manufacture  those  colors  which  he  is  now 
obliged  to  purchase  at  a  very  high  price. 

The  approbation  of  the  profession  will  be 
our  most  satisfactory  reward. 

THE  AUTHOR. 

New  Lebanon,  N.  Y., 

April,  1863. 


CONTENTS. 


CHAPTER  I. 

PAGE 

Historical  notice  of  the  art  of  dyeing    ....  25 
CHAPTER  If. 

Chemical  principles  of  the  art  of  dyeing     •       .  .33 
CHAPTER  III. 

Preliminary  preparation  of  stuffs  .       .       .       .  ,39 
CHAPTER  IV. 

Mordants     .........  43 

CHAPTER  V, 

Dyeing   .  .47 

CHAPTER  VI. 

On  the  coloring  matters  produced  by  coal  tar       .       .  49 

CHAPTER  VII. 
Distillation  of  coal  tar  .       .       .       .       .       .  .52 

CHAPTER  VIII. 

History  of  aniline — Properties  of  aniline — Preparation 
of  aniline  directly  fron  coal  tar        .       .       •  .60 


X 


CONTENTS, 


CHAPTER  IX. 

PAGE 

Artificial  preparation  of  aniline— Preparation  of  benzole 
—Properties  of  benzole— Preparation  of  nitro-benzole 
— Transformation'^  nitro-benzole  into  aniline,  by 
means  of  sulphide  of  ammonium ;  by  nascent  hydro- 
gen]; Ihy  acetate  of  iron  ;  and  by  arsenite  of  potash 
— Properties  of  the  bi-nitro-benzole  .       .  .68 

.*  ? 

CHAPTER  X. 

Aniline  purple — Violine  —  Roseine —  Emeraldine — Bleu 
de  Paris    .........  81 

CHAPTER  XI. 

Futschine,  or  magenta  92 

CHAPTER  XIL 

Coloring  matters  obtained  by  other  bases  from^coal  tar 
— Nitroso-phenyline — Di-nitro-aniline — Nitro-pheny- 
line — Picric  acid — Rosolic  acid — Quinoline      .       .  98 

CHAPTER  XIII. 

Naphthaline  colors — Chloroxynaphthalic  and  perchlo- 
roxynaphthalic  acids — Carminaphtha — Ninaphthala- 
mine  —  Nitrosonaphthaline — Naphthamein — Tar  red 
— Azuline  104 

CHAPTER  XIV. 

Application  of  coal  tar  colors  to  the  art  of  dyeing  and 
calico  printing  .       .       .       .       .       .       .  ,112 


CHAPTER  XV. 
Action  of  light  on  coloring  matters  from  coal  tar  . 


120 


CONTENTS. 


xi 


CHAPTER  XVI. 

PAGE 

Latest  improvements  in  the  art  of  dyeing — Chrysanimio 
acid — Molybdic  and  picric  acids — Extract  of  madder  125 

CHAPTER  XVII. 

Theory  of  the  ligation  of  coloring  matters  in  dyeing  and 
printing    .,.....„.  133 

CHAPTER  XVIIL 
Principles  of  the  action  of  the  most  important  mordants  144 

CHAPTER  XIX. 
Aluminous  mordants    ......  148 

CHAPTER  XX. 
Ferruginous  mordants  .       .       .       .       .       .  .159 

CHAPTER  XXL 
Stanniferous  mordants  .       .       ,       .       .       .  .170 

CHAPTER  XXIL 
Artificial  alizarin   .  .175 

CHAPTER  XXIII. 

Metallic  hyposulphites  as  mordants — Dyer's  soap — Pre- 
paration of  indigo  for  dyeing  and  printing — Relative 
value  of  indigo — Chinese  green— Murexide       .  .179 

t 


(INSTITUTE 


COLORING  MATTERS  FROM  COAL  TAR. 


CHAPTER  I. 

HISTORICAL  NOTICE  OF  THE  ART  OF  DYEING. 

The  art  of  Dyeing  has  been  successfully  prac- 
tised in  the  East  Indies,  Persia,  Egypt,  and  Syria, 
from  time  immemorial.  In  the  Pentateuch,  fre- 
quent mention  is  made  of  linen  cloths  dyed  blue, 
purple,  and  scarlet;  and  of  ram  skins  dyed  red; 
the  works  of  the  Tabernacle,  and  the  vestments 
of  the  High  Priest  were  commanded  to  be  of  pur- 
ple. 

The  Tyrians  were  probably  the  only  people  of 
antiquity  who  made  dyeing  their  chief  occupation, 
and  the  staple  of  their  commerce.  The  opulence 
of  Tyre  seems  to  have  proceeded,  in  a  great  mea- 
sure, from  the  sale  of  its  rich  and  durable  purple. 
It  is  unanimously  asserted  by  all  writers,  that  a 
Tyrian  was  the  inventor  of  the  purple  dye,  about 
1500  years  before  the  birth  of  Christ,  and  that 
the  King  of  Phoenicia  was  so  captivated  with  the 

% 


26 


HISTORICAL  NOTICE. 


color,  that  he  made  purple  one  of  his  principal 
ornaments,  and  that,  for  many  centuries  after,  Ty- 
rian  purple  became  a  badge  of  royalty.  So  highly 
prized  was  this  color,  that  in  the  time  of  Augustus, 
a  pound  of  wool  dyed  with  it,  cost  at  Eome,  a  sum 
nearly  equal  to  thirty  pounds  sterling.  The  Ty- 
rian  purple  is  now  generally  believed  to  have  been 
derived  from  two  different  kinds  of  shell-fish,  de- 
scribed by  Pliny  under  the  names  purpura  and 
huccinum,  and  was  extracted  from  a  small  vessel 
or  sac  in  their  throats  to  the  amount  of  one  drop 
from  each  animal;  but  an  inferior  substance  was 
obtained  by  crushing  the  whole  substance  of  the 
buccinum.  At  first  it  is  a  colorless  liquid,  but  by 
exposure  to  air  and  light  it  assumes  successively  a 
citron-yellow,  green,  azure,  red,  and,  in  the  course 
of  forty-eight  hours,  a  brilliant  purple  hue.  If  the 
liquid  be  evaporated  to  dryness  soon  after  being 
collected,  the  residue  does  not  become  tinged  in 
this  manner.  These  circumstances  correspond 
with  the  minute  description  of  the  manner  of 
catching  the  purple-dye  fish  given  in  the  work  of 
an  eye-witness,  Eudocia  Macrembolitissa,  daughter 
of  the  Emperor  Constantine  the  Eighth,  who  lived 
in  the  eleventh  century.  The  color  is  remarkable 
for  its  durability.  Plutarch  observes,  in  his  life 
of  Alexander,  that,  at  the  taking  of  Susa,  the 
Greeks  found,  in  the  royal  treasury  of  Darius,  a 
quantity  of  purple  cloth,  of  the  value  of  five  thou- 
sand talents,  which  still  retained  its  beauty,  though 


HISTORICAL  NOTICE. 


27 


it  had  lain  there  one  hundred  and  ninety  years. 
This  color  resists  the  action  even  of  alkalies,  and 
most  acids. 

Pliny  states  that  the  Tyrians  gave  the  first 
ground  of  their  purple  dye  by  the  unprepared 
liquor  of  the  purpura^  and  then  improved  or 
heightened  it  by  the  liquor  of  the  buccinum.  In 
this  manner  they  prepared  their  double-dyed  pur- 
ple— purpura  dibapha — which  was  so  called,  either 
because  it  was  immersed  in  two  different  liquors, 
or  because  it  was  first  dyed  in  the  wool  and  then 
in  the  yarn. 

In  ancient  Greece  it  does  not  appear  that  the 
art  of  dyeing  was  much  cultivated.  In  Eome  it 
received  more  attention ;  but  very  little  is  now 
known  of  the  processes  followed  by  the  Eornans, 
such  arts  being  held,  by  them;  in  low  estimation. 
The  principal  ingredients  used  by  these  people 
were  the  following :  Of  vegetal  matters,  alkanet, 
archil,  broom,  madder,  nutgalls,  woad,  and  the 
seeds  of  the  pomegranate,  and  of  an  Egyptian 
acacia;  and  of  mineral  productions,  sulphate  of 
iron,  sulphate  of  copper,  and  a  native  alum  mixed 
with  the  former. 

The  progress  of  dyeing,  as  of  all  other  arts,  was 
completely  stopped  in  Europe, .for  a  considerable 
time,  by  the  invasion  of  the  Northern  barbarians 
in  the  fifth  century.  In  the  East  the  art  still  con- 
tinued to  flourish,  but  it  did  not  revive  in  Europe 
until  towards  the  end  of  the  twelfth  or  the  begin- 


28 


HISTORICAL  NOTICE. 


ning  of  the  thirteenth  century.  One  of  the  places 
chiefly  celebrated  for  this  art  was  Florence,  where, 
it  is  said,  there  were  no  less  than  two  hundred 
establishments  at  work  in  the  early  part  of  the 
fourteenth  century.  A  Florentine  dyer,  having 
ascertained  in  the  Levant  a  method  of  extracting 
a  coloring  principle  from  the  lichens  which  furnish 
archil,  introduced  this  on  his  return,  and  acquired 
by  its  sale  an  immense  fortune. 

The  discovery  of  America  tended  greatly  to  the 
advancement  of  this  art,  as  the  dyers  were  sup- 
plied thence  with  several  valuable  coloring  mate- 
rials previously  unknown;  amongst  which  are 
logwood,  quercitron,  Brazil-wood,  cochineal,  and 
annotto.  About  the  year  1650,  also,  a  great  im- 
provement in  dyeing  took  place,  which  consisted 
in  the  introduction  of  a  salt  of  tin  as  an  occasional 
substitute  for  alum.  With  cochineal,  the  former 
was  found  to  afford  a  color  far  surpassing  in  bril- 
liancy any  of  the  ancient  dyes.  To  Cornelius 
Drebbel  the  merit  of  this  application  is  attributed. 
His  son-in-law  established  an  extensive  dye-house 
at  Bow,  near  London,  about  the  year  1563. 

For  several  centuries  the  Italians,  and  par- 
ticularly the  Venetians,  prosecuted  the  art  of 
dyeing  to  a  large  extent,  and  long  held  a  complete 
monopoly  of  the  art,  and  procured  large  sums  by 
it  from  other  nations.  In  the  year  1548,  one  John 
Ventura  Eosetti  published  a  book,  termed  PlicthoJs 
Art  of  Dyeing ,  in  which  he  teaches  how  to  give  to 


HISTORICAL  NOTICE.  29 

cloth,  linen,  cotton  and  silk,  real  and  beautiful, 
as  well  as  false  and  common  dyes,  which  is,  per- 
haps, the  first  book  that  ever  appeared  upon  the 
subject,  and  laid  the  first  foundation  for  the  im- 
provement of  this  art  which  afterwards  took  place; 
it  having  excited  the  French,  English,  and  Germans 
to  apply  in  earnest,  in  their  different  countries,  to 
improving  so  useful  and  extensive  a  branch  of 
manufacture. 

After  this  period  the  art  was  extensively  carried 
on  by  the  Flemings,  and  many  of  them  emigrating 
to  Germany,  France,  and  England,  established 
themselves  as  dyers,  and  thus  gave  great  impetus 
to  its  advancement.  In  1667,  a  Fleming  named 
Brauer  came  to  England  with  his  whole  family, 
and  brought  the  dyeing  of  woollen  there  to  that 
degree  of  perfection  at  which  it  has  been  ever  since 
maintained.  Shortly  after  this  several  works  were 
published  upon  the  art,  which  did  much  to  im- 
prove it  and  make  it  more  cultivated. 

Logwood  and  indigo  began  to  be  employed  as 
dyes  in  Europe  about  the  middle  of  the  sixteenth 
century,  but  not  without  considerable  opposition 
from  the  cultivators  of  the  native  woad ;  the  former 
were  prohibited  in  England  by  Queen  Elizabeth, 
under  a  very  heavy  penalty,  and  all  found  in  the 
country  was  ordered  to  be  destroyed:  their  use 
was  not  permitted  till  the  reign  of  Charles  the 
Second. 

Indigo,  the  innoxious  and  beautiful  product  of 

3* 


30 


HISTORICAL  NOTICE. 


an  interesting  tribe  of  tropical  plants,  which  is 
adapted  to  form  the  most  useful  and  substantial 
of  all  dyes,  was  actually  denounced  as  a  dangerous 
drug— food  for  the  devil,  it  was  called — and  for- 
bidden by  Parliament,  in  the  reign  of  Elizabeth, 
to  be  used.  An  act  was  passed,  authorizing 
searchers  to  burn  both  it  and  logwood  in  every 
dye-house  where  they  could  be  found,  and  this 
act  remained  in  full  force  till  the  time  of  Charles 
the  Second,  a  period  embracing  a  considerable  part 
of  a  century.  A  foreigner  might  have  supposed 
that  the  legislators  of  England  entertained  such 
an  affection  for  their  native  woad,  with  which 
their  denuded  sires  used  to  stain  their  skins  in 
the  olden  times,  that  they  would  allow  no  out- 
landish drug  to  come  in  competition  with  it.  A 
most  instructive  and  interesting  volume  might  be 
written,  illustrative  of  the  evils  inflicted  upon  arts, 
manufactures,  and  commerce,  in  consequence  of 
the  ignorance  of  lawgivers. 

When  these  absurd  prejudices  were  gradually 
overcome  in  .the  eighteenth  century,  the  art  of 
dyeing  made  considerable  progress.  Madder,  from 
which  the  color  known  as  Turkey  or  Adrianople 
red  is  produced,  then  began  to  be  properly  appre- 
ciated; and  quercitron,  a  fine  yellow  dye,  was 
brought  extensively  into  notice  by  Dr.  Bancroft. 
But  the  chief  improvements  of  the  moderns  in 
this  art,  consist  in  the  employment  of  pure  mor- 
dants, and  in  the  application  of  colors  derived 


HISTORICAL  NOTICE. 


31 


from  mineral  compounds,  as  sesquioxide  of  iron, 
prussian -blue,  chrome-yellow,  chrome-orange,  man- 
ganese-brown, etc.  Each  of  these  may  be  obtained 
as  an  insoluble  precipitate,  by  mixing  together 
two  dissolved  salts;  in  the  dyeing  processes,  the 
proper  solutions  are  made  to  mingle,  and  produce 
the  deposit  within  the  fibre  by  impregnating  first 
with  one  solution  and  afterwards  with  the  other. 
As  the  precipitate  thus  produced  is  imprisoned 
within  the  fibre,  it  is  not  removable  by  mere 
aspersion  with  water. 

In  India,  was  discovered  the  mode  of  dyeing 
Turkey  red,  which  is  the  most,  durable  vegetal 
tint  known.  It  was  afterwards  practised  in  other 
parts  of  Asia  and  in  Greece;  and  about  the  middle 
of  last  century,  dye-works  for  this  color  were 
established  near  Eouen  and  in  Languedoc  by 
several  Greeks.  In  1765  the  French  government, 
convinced  of  the  importance  of  the  process,  caused 
an  account  of  it  to  be  published;  but  it  was  not 
introduced  into  England  until  the  end  of  the 
eighteenth  century,  when  a  Turkey-red  dye-house 
was  established  in  Manchester  by  M.  Borelle,  who 
obtained  a  grant  from  government  for  the  disclo- 
sure of  his  process.  The  method,  which  was  made 
public,  does  not  seem  to  have  been  very  successful. 
A  better  mode  was  introduced  into  Glasgow  about 
the  same  time  by  another  Frenchman,  named 
Papillon.  Previous  to  this,  however,  Mr.  Wilson 
•of  Ainsworth,  near  Manchester,  had  obtained  the 


32 


HISTORICAL  NOTICE. 


secret  from  the  Greeks  at  Smyrna,  which  he  re- 
vealed; but  the  process  was  said  to  be  expensive, 
tedious,  and  less  applicable  to  manufactured  goods 
than  to  cotton  in  the  skein.  The  greater  part  of 
the  Turkey-red  dyeing  executed  in  Great  Britain, 
is  still  carried  on  in  Glasgow. 


THE  ART  OF  DYEING. 


S3 


CHAPTER  II. 

CHEMICAL  PRINCIPLES  OF  THE  ART  OF  DYEING. 

The  art  of  dyeing  has  been  of  late  so  scientifi- 
cally cultivated  that  it  would  require  a  greater 
space  than  the  limits  of  this  treatise  can  afford,  to 
give  a  complete  idea  of  it,  and  we  shall  confine 
ourselves  to  the  explanations  of  the  chemical 
principles,  on  which  are  based  the  preliminary  pre- 
parations of  the  textile  fibres  to  render  them  fitted 
for  the  manufacture  of  tissue  and  those  on  which 
is  founded  the  art  of  fastening  coloring  matters. 

Preparation  of  the  Textile  Fibres. 

The  textile  fibres  used  in  manufactures  are 
either  of  vegetable  or  animal  origin;  the  first 
being  chiefly  Hemp,  Flax,  and  Cotton,  and  the 
second  wool,  hair  of  animals,  and  silk  spun  by  the 
silk  worm. 

Cotton  is  nearly  pure  lignin,  while  hemp  and 
flax  are  composed  of  lignin  in  long  filaments, 
which,  when  dry,  adhere  to  each  other  by  means 
of  a  gelatinous  substance  called  Pectin,  although 
it  differs  probably  from  that  found  in  fruits,  and 
which  must  be  removed  to  render  them  fit  for 


34 


THE  ART  OF  DYEING. 


spinning  and  weaving.  For  this  purpose  they  are 
rotted,  which  operation  consists  in  plunging  them 
tied  in  bundles,  into  water,  where  they  are  left, 
until  fermentation  commences,  which  is  manifested 
in  stagnant  waters,  by  a  very  disagreeable  odor ; 
the  bundles  are  then  withdrawn  from  the  rotting 
pond,  and,  after  having  been  dried  in  the  air,  are 
subjected  to  a  mechanical  operation  of  which  the 
object  is  to  detach  the  foreign  substances,  which 
have  become  friable  by  the  desiccation*  ensuing  on 
the  rotting,  and  to  isolate  the  fibres.  Hemp  and 
flax  thus  prepared  are  fit  to  be  connected  by 
spinning  into  unbleached  thread,  which  may  be 
immediately  used  for  weaving  cotton,  undergoes 
no  preliminary  preparations,  and  may  be  imme- 
diately spun  and  woven. 

Wool,  as  it  is  found  on  the  living  animal,  is  im- 
pregnated with  a  considerable  quantity  of  foreign 
matters,  commonly  called  grease  (suint),  and  which 
consists  essentially  of  substances  soluble  in  water, 
and  fatty  substances  insoluble  in  that  fluid.  Sheep 
are  usually  washed  before  being  shorn,  and  then 
yield  what  is  called  washed  wool,  which  has  just 
lost  a  large  portion  of  its  soluble  matters,  and  a 
portion  of  the  fatty  matters,  which  separated  in 
the  state  of  an  emulsion.  Wool  which  has  not 
undergone  this  operation  is  called  unwashed  wool, 
and  the  process  by  which  the  grease  is  removed 
from  wool  is  known  by  the  name  of  scouring.  Un- 
washed is  scoured  with  wash  wool  in  a  bath  of  84 


• 


THE  ART  OF  DYEING.  35 

gallons  of  water,  and  20  to  22  gallons  of  putrefied 
urine,  the  whole  being  heated  at  122°  or  140°  for 
soft  wool,  and  to  158°  or  167°  for  harsh  wool;  after 
dipping  6  lbs.  12  oz.  or  9  lbs.  of  unwashed  wool 
into  the  bath,  and  stirring  it  with  a  stick  for  10 
minutes,  they  are  removed  and  allowed  to  drain 
over  the  kettle,  the  same  being  done  with  another 
lot,  until  about  90  lbs.  in  all  have  been  thus 
treated ;  1 J  galls,  to  2  galls,  of  putrid  urine  are 
then  added,  and  112  lbs.  of  washed  wool  passed 
through  it,  which  is  scoured  both  by  the  carbonate 
of  ammonia  of  the  putrefied  urine  and  the  alka- 
line substance  yielded  by  the  unwashed  wool. 
The  same  operation  is  repeated  on  a  new  lot  of  90 
lbs.  of  washed  wool,  after  which  a  new  dose  of  1  J 
to  2  galls,  of  putrid  urine  is  added,  and  45  lbs.  of 
unwashed  wool,  washed  in  it.  This  alternate 
scouring  of  wash  and  unwashed  wool  is  continued 
during  the  whole  clay,  adding  urine  at  each  fresh 
quantity  of  unwashed  wool.  After  this  operation 
the  unwashed  wool  should  be  considered  as  wash, 
and  treated  accordingly. 

When  the  wool  scourer  has  no  unwashed  wrool; 
he  makes  his  bath  of  183  galls,  of  water  and  84 
galls,  of  urine,  heats  it  at  120°  or  140°  and  passes 
through  it  68  lbs.  of  wool  in  5  lots,  each  of  which 
he  leaves  in  the  bath  for  12  or  15  minutes,  after 
which  he  adds  2  pints  of  water  and  \  gall,  of 
urine,  and  then  scours  an  additional  portion  of  68 


36 


THE  ART  OF  DYEING. 


lbs.  of  wool,  &c.  Some  scourers  add  marly  clay 
to  the  bath. 

"Wash  wool  contains  less  than  15  per  cent,  of 
grease,  while  unwashed  contains  much  more,  and 
by  washing,  scouring,  and  drying  loses  as  much  as 
60  or  70  per  cent,  of  its  weight.  "When  the  washed 
wool  contains  less  than  5  per  cent,  of  grease, 
it  is  scoured  with  soap  or  carbonate  of  soda. 

The  nature  of  the  fatty  matters  of  the  grease  is 
peculiar,  and  they  have  been  called  by  Mr.  Chev- 
reul  stearerin  and  elaierin;  the  first  is  solid,  but 
uncrystallizable,  the  second  is  oleaginous.  These 
fats  are  not  saponified  by  weak  alkalies,  but  when 
they  are  boiled  for  a  long  time  with  a  solution  of 
caustic  potash,  the  liquid  is  found  to  contain  two 
salts  of  potash,  formed  by  peculiar  fat  acids  which 
have  been  called  steareric  and  elaieric  acids,  while 
nothing  analogous  to  glycerin  Jias  been  found,  the 
oxygen  of  the  air  may  possibly  have  some  share 
in  the  formation  of  these  fat  acids. 

After  scouring,  the  wool  is  washed  in  river 
water,  in  willow  baskets.  When  it  is  intended  to 
be  perfectly  white,  it  is  exposed  for  some  time  in 
a  moist  state  in  rooms  in  which  sulphur  is  burned, 
where  the  sulphurous  acid  finishes  the  bleaching, 
and  the  excess  of  it  is  removed  by  fresh  washings. 
It  is  important  not  to  prolong  too  much  the  action 
of  the  sulphurous  acid,  because  it  exerts  a  decom- 
posing agency  on  the  nitrogenous  substance  of  the 
wool. 


THE  ART  OF  DYEING. 


37 


Wool  contains  a  proximate  sulphuretted  prin- 
ciple, which  may  be  separated  by  successive 
immersions  in  lime-water.  Wool  which  has 
been  heated  with  a  weak  alkaline  solution,  disen- 
gages sulphydric  acid,  when  it  is  again  heated 
with  acidulated  water,  and  is  blackened  when 
boiled  with  a  solution  of  a  salt  of  lead  or  prot- 
oxide of  tin. 

Raw  Silk,  as  obtained  from  the  cocoons,  is  im- 
pregnated with  a  gelatinous  substance,  which 
makes  it  very  stiff,  and  generally  gives  it  a  golden 
yellow  tinge.  This  substance,  which  forms  about 
Jth  of  the  weight  of  raw  silk,  dissolves  readily  in 
alkaline  liquids,  but  as  caustic  alkalies  attack  the 
silk  itself,  soap  is  almost  always  used,  and  some- 
times, but  rarely,  carbonate  of  soda. 

The  operation  which  is  called  Scouring  (De- 
CREUSAGe)  the  silk,  is  divided  into  three  stages,  the 
ungumming  (degommage),  boiling,  and  bleaching. 
The  ungumming  is  done  in  a  tin  boiler  containing 
for  every  100  parts  of  silk,  1800  or  2500  parts  of 
water,  and  80  of  soap.  It  is  first  boiled  to  dissolve 
the  soap,  and  then  cold  water  is  added  so  as  to 
lower  the  temperature  at  about  200°,  when  the 
silk  is  dipped  into  it  in  skeins,  supported  by  sticks 
called  lisoirSj  being  there  left  until  all  the  gelati- 
nous matter  is  dissolved,  and  afterwards  wound 
on  a  bobbin.  This  operation  lasts  from  f  to  1J 
hours.  Several  skeins  are  then  united,  forming  a 
hank,  which  is  boiled  for  1J  hours  in  a  bath  con- 
4 


38 


THE  ART  OF  DYEING. 


taining  20  or  30  parts  of  soap  for  2000  parts  of 
water,  which  constitute  the  boiling  (Cuite).  The 
hanks  are  undone,  twisted  into  skeins,  wound  on 
a  bobbin,  and  then  washed  in  a  weak  solution  of 
carbonate  of  soda,  and  in  water.  The  bleaching 
consists  in  dipping  the  silk  held  by  the  lisoirs, 
into  a  bath  heated  at  203°,  and  composed  of 
84  galls,  of  water,  and  from  1  lb.  2  oz.  to  1  lb.  12 
oz.  of  white  Marseilles  soap.  Silks  which  are  in- 
tended to  be  white,  are  exposed  in  addition  to 
sulphurous  acid. 


PREPARATION  OF  STUFFS. 


39 


CHAPTER  III. 

PRELIMINARY  PREPARATION  OF  STUFFS. 

Before  being  printed,  cotton  stuffs  are  singed 
with  the  intention  of  removing  the  filaments 
which  project  from  the  tissue.  The  shearing  is 
performed  by  machines  called  shearing  machines, 
composed  of  two  revolving  cylinders,  one  of 
which,  furnished  with  brushes,  raises  the  nap, 
while  the  other,  provided  with  knives  arranged 
spirally,  shears  it.  In  singing,  the  stuff  is  passed 
rapidly  over  a  metallic  cylinder,  heated  to  nearly 
a  white  heat,  which  burns  off  the  down.  Cotton 
stuffs  intended  to  be  perfectly  white,  are  previously 
bleached,  which  operation  is  also  more  or  less 
completely  performed  on  goods  which  are  to  be 
printed. 

Linen  and  cotton  goods  are  bleached  by  two 
processes :  1.  By  washing  them  in  alkaline  lyes, 
and  exposing  them  on  the  grass.  2.  By  chlorine 
and  by  the  alkaline  hypochlorites. 

The  first  is  the  oldest,  and  was  used  par- 
ticularly for  bleaching  flax  and  hemp  goods.  It 
is  divided  into  the  following  operations :  1.  Scour- 
ing, which  consists  in  dipping  the  stuffs  for  twenty- 


40 


PREPARATION  OF  STUFFS. 


four  hours  in  a  weak  solution  of  caustic  potash, 
heated  at  about  99 °,  washing,  and  then  boiling 
them  for  twenty  minutes  in  the  same  alkaline 
lye. 

2.  The  boiling,  which  consists  in  boiling  the 
scoured  stuffs,  after  having  washed  them  in  water, 
and  compressed  them  between  cylinders. 

3.  Bleaching,  which  consists  in  boiling  them  for 
six  hours  with  an  alkaline  lye  containing  1  part 
of  caustic  potash  for  16  parts  of  stuff,  washing 
them,  and  exposing  them  for  five  or  six  hours  on 
the  grass;  the  alkaline  washings  and  exposure  on 
the  grass  being  renewed  until  the  stuffs  are  per- 
fectly bleached.  During  the  exposure  on  the 
grass,  the  coloring  matters  are  bleached  by  the 
influence  of  the  solar  rays  and  moisture;  the 
absorption  of  oxygen  converting  them  into  new 
substances,  more  readily  soluble  in  the  alkaline 
liquors.  Lastly,  the  stuffs  are  passed  through 
water  heated  at  105°  or  120°,  containing  about 
q\  of  sulphuric  acid,  which  dissolves  the  metallic 
oxides,  after  which  they  are  washed  and  calen- 
dered. 

This  process  requires  a  great  length  of  time, 
and  bleaching  by  the  hypochlorites  or  chlorine 
is  more  expeditious.  The  chlorine  acting  on  the 
coloring  matter  in  the  presence  of  the  water,  de- 
composes this  water  into  hydrogen  and  oxygen ; 
hydrogen  combines  with  the  chlorine  to  form 
hydrochloric  acid,  while  oxygen  in  the  nascent 


PREPARATION  OF  STUFFS. 


41 


state  oxidizes  the  resinous  and  coloring  matters, 
and  renders  them  soluble  in  alkaline  lyes.  The 
hypochlorites  are  reduced  to  the  state  of  chlo- 
rides, and  act  at  the  same  time  by  means  of  the 
nascent  oxygen  given  off  by  the  hypochlorous  acid 
and  the  base,  while  the  concurrence  of  an  acid 
effecting  the  decomposition  of  the  hypochlorites 
hastens  the  bleaching.  Thus  in  both  processes  it 
is  in  the  end  always  an  oxidizing  action,  which 
effects  the  bleaching  and  destruction  of  the  foreign 
substances. 

Hypochlorite  of  lime,  dissolved  in  water,  is 
now  solely  used  in  bleaching,  and  it  is  preferable 
to  all  dilute  solutions,  because  it  is  less  liable  to 
injure  the  ligneous  fibre  of  the  tissue,  although 
the  bleaching  then  requires  more  time. 

The  stuffs,  after  being  passed  over  the  heated 

cylinder  to  be  singed,  are  immediately  dipped 

into  a  vat  filled  with  water  to  cool  them,  where 

they  then  remain  for  twenty-four  hours,  and  lose 

a  considerable  portion  of  their  soluble  principles. 

They  are  then  to  be  perfectly  dried,"  either  by 

being  beaten  or  compressed  between  cylinders, 

and  then  kept  for  twelve  hours  in  a  vat  filled 

with  water  heated  by  steam,  where  they  are 

arranged  in  alternate  layers  with  slaked  lime; 

after  being  again  beaten,  they  are  left  for  twelve 

hours  in  a  lye  of  caustic  soda,  consisting  for  300 

parts  of  stuffs,  of  10  parts  of  caustic  soda  for 

1500  of  water.    This  lye  is  replaced  by  another 

4* 


42 


PREPAEATION  OF  STUFFS. 


containing  only  7.5  of  soda,  which  is  also  allowed 
to  act  for  twelre  hours ;  after  which  the  stuffs, 
pressed  dry,  are  passed  through  the  hypochlorite 
of  lime,  and  then  through  sulphuric  acid.  The 
bath  of  hypochlorite  generally  contains  0.15 
parts  of  chlorine  or  a  quart  of  water ;  and  the 
stuffs  after  being  immersed  in  it  are  passed  be- 
tween two  wooden  cylinders,  descending  them 
immediately  into  a  bath  acidulated  with  sulphuric 
or  hydrochloric  acid,  which  hastens  the  bleaching 
by  isolating  the  hypochlorous  acid. 

After  being  washed  in  fresh  water,  they  are  for 
a  second  time  subjected  to  the  action  of  alkaline 
lyes,  hypochloride  of  lime,  and  the  acid  baths,  and 
lastly,  after  another  washing  in  fresh  water,  they 
are  dried  in  washing  machines,  and  more  body  is 
given  to  them  by  dressing  them  with  starch. 


MORDANTS. 


43 


CHAPTER  IV. 

MORDANTS. 

The  tissues  of  muslin  or  linen  stuffs  have,  for 
a  great  number  of  coloring  substances,  an  affinity 
sufficiently  powerful  to  fasten  them  on  their  sur- 
faces, and  to  acquire  a  deep  color,  while  the  com- 
bination is  nearly  strong  enough  to  enable  them 
to  resist  washing;  particularly  with  alkaline  soaps. 
They  are  made  fast,  and  at  the  same  time  the 
color  is  heightened  by  previously  depositing  on 
the  tissues  certain  substances  which  have  a  greater 
affinity  for  these  tissues  than  the  coloring  matter, 
and  which  possess,  at  the  same  time,  the  pro- 
perty of  forming,  with  the  coloring  matters,  com- 
pounds sufficiently  fixed  to  resist  washing  in  fresh 
water  and  in  soapsuds.  These  substances  which 
thus  play  an  intermediate  part  between  the  woven 
fabrics  and  the  coloring  matters,  are  called  mor- 
dants. The  affinities,  by  virtue  of  which  they  are 
fastened  on  the  fabric,  exhibit  this  essential  dif- 
ference from  those  observed  in  ordinary  chemical 
operations,  that,  in  the  latter,  combination  gene- 
rally ensues  only  between  disaggregated  sub- 
stances, and  if  one  of  the  substances  is  originally 


44 


MORDANTS. 


aggregated,  it  becomes  disaggregated  by  the 
simple  fact  of  combination ;  while,  in  dyeing,  the 
woven  fabric  retains  its  form  and  consistence, 
without  being  in  the  slightest  degree  disaggre- 
gated by  the  mordants  and  coloring  matters. 
Certain  mordants  do  not  change  the  shade  of  the 
coloring  matters,  such,  for  example,  as  the  salts 
of  alumina  and  chloride  of  tin;  while  others, 
on  the  contrary,  alter  the  color,  as  the  salts  of 
iron,  copper,  manganese.  The  salts  of  alumina, 
used  as  mordants,  are  the  sulphate  and  acetate  of 
alumina  and  alum  ;  the  fastening  of  color  by  alum 
being  called  aluming. 

In  order  to  alum  cotton,  flax,  or  hempen  stuffs, 
they  are  left  for  twenty-four  hours  in  a  tepid  bath, 
containing  one  pound  of  alum  for  six  pounds  of  * 
fabric,  when  a  portion  of  the  alum  adhering  to 
the  stuff,  renders  the  latter  fit  for  dyeing.  For 
dark  colors,  the  ordinary  commercial  alum  is 
used ;  pure  alum  being  preferred  for  bright  colors, 
because  common  altfm  contains  a  small  quantity 
of  sulphate  of  iron,  which  would  modify  the 
color. 

Wool  is  alumed  by  being  first  boiled  in  bran- 
water  for  an  hour,  and  washed  in  fresh  water,  and 
then  kept  for  two  hours  in  a  boiling  solution 
which  contains  ten  to  fifteen  per  cent,  of  alum,  a 
small  quantity  of  cream  of  tartar  being  generally 
added,  which  facilitates  the  deposit  of  alumina  on 
the  tissue,  probably  in  converting  a  portion  of  the 


MORDANTS. 


45 


sulphate  of  alumina  into  a  tartrate  more  easy  to 
decompose.  When  the  wool  is  alumed,  it  is  left 
for  two  days  to  rest  before  dyeing,  in  order  to 
render  the  combination  of  the  mordant  with  the 
fibre  more  intimate. 

Silk  is  alumed  when  cold,  by  keeping  it  for 
fifteen  or  sixteen  hours  in  a  bath  containing  ^  of 
alum,  after  which  it  is  removed  and  washed. 
Acetate  of  alumina,  which  is  often  used  as  a  mor- 
dant for  ligneous  stuffs,  and  for  certain  colors,  is 
prepared  like  we  shall  see  hereafter,  by  decom- 
posing alum  by  acetate  of  lead.  The  solution  of 
acetate  of  alumina  thus  obtained  being  generally 
thickened  with  gum  or  starch. 

Stuffs  of  lignin,  mordanted  with  alum,  are 
again  subjected,  before  being  dyed,  to  another 
operation,  the  effect  of  which  is  not  well  under- 
stood; they  are  immersed  for  some  time  in  two 
baths  of  water,  containing  from  six  to  eight  per 
cent,  of  cow-dung.  To  the  first  of  these  baths  a 
certain  quantity  of  chalk  is  added,  the  intention  of 
which  appears  to  be  to  saturate  the  acid  partly 
adhering  to  the  tissue  with  the  mordant;  while 
the  second  contains  only  water  and  dung.  The 
temperature  of  these  two  baths  varies  according 
to  the  nature  of  the  stuffs  and  that  of  the  mor- 
dants. The  cow-dung  appears  to  act  by  means 
of  the  phosphates  it  contains,  for  a  mixture  of 
phosphate  of  soda  and  lime  can  be  substituted 
for  it, 


46 


MORDANTS. 


Protochloride  of  tin  is  chiefly  used  for  obtain- 
ing the  oxide  of  tin  as  a  mordant,  which  adheres 
very  firmly  to  the  tissues.  Bichloride  of  tin  is 
often  used  for  freshing  colors,  particularly  those 
of  cochineal  and  madder. 

The  mordant  of  oxide  of  iron  is  furnished  by 
the  proto-acetate,  prepared  by  the  action  of  pyro- 
ligneous  acid  on  old  iron. 

The  question  of  mordants  is  so  important,  that 
we  will  treat  it  hereafter  at  some  length. 


DYEING. 


47 


CHAPTER  V. 

DYEING. 

After  the  stuffs  are  mordanted,  they  are  .im- 
mersed in  order  to  be  dyed,  in  solutions  of  color- 
ing matters  of  various  temperatures,  and  then 
left  for  a  longer  or  shorter  time,  according  to  the 
nature  of  the  stuff  and  the  tint  of  color  to  be 
obtained.  It  is  essential  that  all  parts  of  the  fabric 
should  remain  the  same  length  of  time  in  the  dye; 
to  which  effect  it  is  rolled  around  a  wooden  roller 
suspended  under  the  dye  tub,  and  is  unrolled 
through  the  tub,  this  process  being  continued 
until  the  color  has  obtained  the  shade  required. 
In  order  to  obtain  a  regular  shade,  it  is  better  to 
use  successive  baths  of  different  strength,  com- 
mencing with  the  weakest.  The  baths  are  some- 
times composed  of  a  single  coloring  matter,  and 
sometimes  of  a  mixture  of  several,  while  at  other 
times  the  stuff  is  passed  successively  through  two 
baths  containing  different  colors,  and  thus  an  in- 
termediate shade  is  obtained ;  the  colors  are  fast- 
ened by  washing  in  soapsuds  or  in  other  solutions. 


48 


DYEING. 


It  would  lead  us  too  far  to  give  a  description  of 
the  methods  of  preparing  the  different  solutions 
for  dyeing  and  the  manipulations  of  the  process. 
For  this  we  refer  the  reader  to  a  regular  work  on 
the  art  of  dyeing. 


COLORING  MATTERS  PRODUCED  BY  COAL  TAR.  49 


CHAPTER  VI. 

ON  THE  COLORING  MATTERS  PRODUCED  BY  COAL 
TAR. 

History. — Until  the  year  1854,  Aniline  was 
known  only  by  chemists;  it  was  a  product  of  the 
laboratory  which  was  found  only  with  difficulty; 
still,  Industry  had  not  the  less  desire  to  use  it,  on 
account  of  its  high  price  and  its  difficult  and  costly 
preparation.  At  that  time,  Mr.  Dumas  presented 
to  the  Academy  of  Science  of  Paris  a  paper  on  a 
new  method  of  formation  of  artificial  organic  bases,  in 
which  Mr.  Bechamp  made  known  a  process  by 
which  he  was  enabled  to  obtain  Aniline  not  only 
easily,  but  also  at  a  low  price. 

By  the  efforts  of  Messrs.  Eenard  Brothers,  Franc, 
Tabourin  and  Bechamp,  Aniline  is  now  a  product 
which  can  be  obtained  easily. 

In  1826,  Unverdorben,  studying  the  products 
which  result  from  the  dry  distillation  of  animal 
matters  with  indigo,  discovered  among  the  pyro- 
geneous  products  of  this  last  substance,  an  organic 
basis,  volatile,  liquid,  and  heavier  than  water, 
which  he  called  Crystalline,  because  with  mineral 
acids  it  produces  easily  crystallized  salts. 
5 


50     COLORING  MATTERS  PRODUCED  BY  COAL  TAR. 


Mr.  Fritzsche  afterwards  studied  these  products, 
and  called  Aniline  (from  the  name  of  the  indigofera 
anil)  the  basis  obtained  in  distilling  indigo  with 
caustic  potash.  He  demonstrated  that  this  basis 
was  identical  to  Crystalline.  Subsequently  Mr. 
Eunge  isolated,  by  a  process  modified  by  Hoffmann, 
among  the  bases  which  exist  in  the  heavy  oils  of 
the  distillation  of  coal  tar,  an  oily  organic  basis 
from  which  he  developed  a  fine  violet  blue  color 
by  hypochlorite  of  lime. 

Mr.  Zinin  afterwards,  by  the  action  of  sulphuret 
hydrogen  on  nitro-benzine  in  connection  with 
ammonia,  produced  an  organic  basis  which  he 
called  Benzidum. 

When  the  identity  of  all  these  products  was 
established,  chemists  adopted  the  name  of  Aniline 
to  designate  them  all,  this  title  being  the  best  for 
the  formation  of  compound  names. 

These  first  experiments  gave  birth  to  others 
which  showed  that  in  a  multitude  of  reactions, 
Aniline  could  be  produced,  so  it  could  be  formed 
by  the  action  of  alkalies  and  alcohol  on  nitro- 
benzine. 

Messrs.  Laurent  and  Hoffmann,  in  heating  for 
fifteen  days,  in  a  tube,  phoenic  acid  with  ammonia, 
have  also  produced  Aniline. 

During  all  the  time  that  this  product  could  be 
made  only  by  the  above  processes,  Aniline  was 
simply  an  object  of  curiosity.    Its  extraction  from 


COLORING  MATTERS  PRODUCED  BY  COAL  TAR.  51 

coal  tar  was  difficult,  and  from  indigo,  the  quantity 
produced  was  too  small  and  too  costly. 

Mr.  Perkins,  the  great  English  manufacturer, 
studied  the  production  of  Aniline  at  the  same  time 
as  several  French  chemists,  but  the  French  being 
too  much  engaged  with  the  theoretical  question, 
left  to  Mr.  Perkins  the  honor  of  the  industrial  dis- 
covery. It  was  with  the  benzine  (benzole)  that 
he  succeeded  in  producing  the  largest  quantities 
of  Aniline. 


52 


DISTILLATION  OF  COAL  TAB. 


CHAPTER  VII. 

DISTILLATION  OF  COAL  TAR. 

The  dry  distillation  of  organic  matters,  vege- 
table or  animal,  from  the  great  variety  of  products 
to  which  it  gives  rise,  constitutes  one  of  the  most 
interesting  operations  of  chemistry. 

Their  reactions  are  very  complex,  and  some  of 
them  have  been  very  little  studied,  as  indeed  is 
the  case  with  many  of  the  substances  formed. 

If  the  body  submitted  to  dry  distillation  could 
be  maintained  during  the  operation  under  uniform 
conditions  of  desiccation,  temperature,  and  pres- 
sure, the  reactions  and  the  products  would  be 
more  simple.  If,  for  example,  wood  be  heated 
very  slowly  in  close  vessels,  first  to  212°  F.,  then 
to  392°  and  572°,  and  so  on,  there  is  at  first  dis- 
engaged almost  pure  water,  then  impure  strong 
acetic  acid,  and  afterwards  a  mixture  of  acetone 
and  acetate  of  methylene;  the  maximum  of  char- 
coal is  left  as  residue,  and  the  least  amount  of  tar 
and  gas  is  produced,  the  latter  consisting  only  of 
carbonic  acid  and  carburetted  hydrogen. 

In  practice,  however,  when  wood  is  distilled  in 
iron  cylinders,  heated  from  the  outside,  the  heat 


DISTILLATION  OF  COAL  TAR. 


53 


only  penetrates  to  the  interior  gradually.  The 
outside  layers  are,  therefore,  the  first  decomposed; 
they  at  first  lose  water,  then  furnish  pyroligneous 
acid  and  wood  spirit,  at  the  same  time  giving  off 
carbonic  acid  and  a  little  carburetted  hydrogen. 

The  inner  layers  in  turn  are  similarly  decom- 
posed, but  the  products  as  they  are  given  off  are 
brought  into  contact  with  the  outer  layer,  already 
in  a  more  advanced  state  of  decomposition  and  at 
a  much  higher  temperature,  and  hence  new  reac- 
tions take  place  and  new  products  are  formed. 
Thus,  the  vapor  of  water  in  contact  with  red  hot 
charcoal  is  decomposed,  and  forms  carbonic  acid 
and  hydrogen;  a  part  of  the  carbonic  acid  is  again 
decomposed  by  the  red  hot  carbon  to  form  some 
oxide  of  carbon.  A  part  of  the  nascent  hydrogen 
combines  with  carbon  to  form  various  hydro- 
carbons; one  part  of  the  acetic  acid  is  decomposed 
by  the  high  temperature  to  form  acetone  and  car- 
bonic acid;  another  part  reacts  on  the  wood  spirit, 
and  forms  methylic  acetate;  a  fraction  of  the  wood 
spirit  and  acetone  are  also  decomposed,  producing 
tarry  matters,  pyroxanthine,  oxyphenic  acid,  duma- 
sine,  etc.  To  these  must  be  added  the  influence 
of  certain  nitrogenized  bodies,  and  we  can  under- 
stand how  all  these  compounds,  successively 
formed  under  the  most  favorable  circumstances 
for  acting  on  one  another,  since  they  are  in  the 
nascent  state  and  exposed  to  a  high  temperature, 
may  give  rise  to  the  formation  of  a  great  variety 

5* 


54  DISTILLATION  OF  COAL  TAR. 


of  different  compounds,  which  will  be  set  free 
either  in  the  state  of  a  permanent  gas  or  of  a 
condensable  vapor,  and  leave  fixed  carbon  as  a 
residue. 

The  same  takes  place  whether  wood,  coal, 
asphalte,  peat,  resin,  oils,  or  animal  matters  be 
distilled;  but  it  is  evident  that  the  original  com- 
position of  the  material  submitted  to  dry  distilla- 
tion must  powerfully  influence  the  nature  and 
composition  of  the  products.  In  those  which, 
like  wood,  are  rich  in  oxygen  and  poor  in  nitro- 
gen, the  pyrogeneous  products  contain  much 
acetic  acid  and  but  little  ammonia,  and  conse- 
quently have  an  acid  reaction ;  on  the  contrary, 
the  matters  containing  much  nitrogen,  and  but 
little  oxygen,  like  coal  and  animal  matters;  give 
rise  to  the  formation  of  much  ammonia,  and  the 
products  have  an  alkaline  reaction. 

In  this  division  we  intend  only  to  confine  our 
attention  to  the  products  obtained  by  the  distilla 
tion  of  coal  tar  from  gas  works.  Considerable 
differences  are  noticed  in  the  composition  of  the 
tar  procured  from  different  qualities  of  coal  and 
schists,  according  to  the  rapidity  with  which  the 
distillation  has  been  conducted.  Some  tars,  for 
instance,  contain  but  little  benzole,  but  much 
naphthaline;  boghead  tar  is  rich  in  paraffine; 
others  contain  a  preponderating  quantity  of 
phenyl  and  benzole. 


DISTILLATION  OF  COAL  TAR. 


55 


Table  of  the  Products  Obtained  by  Distillation  and 
Rectification  of  Coal  Tar. 
Solid  Products. 


Carbon, 

Naphthaline, 

Paranaphthaline 


or  Anthraceine, 
Paraffine, 

Liquid  Products. 


Chrysene, 
Pyrene. 


Acids. 
Rosolic, 
Brunolio, 
Phenic, 
Phenol, 
Acetic, 
Buthyric. 


Neutrals. 
Water, 

Essence  of  Tar, 

Light  Oil  of  Tar, 

Heavy  Oil  of  Tar, 

Benzole, 

Toluole, 

Cuinole, 

Cymole, 

Propyle, 

Butyl  e, 

Amyle, 

Caproyle, 

Heptylene, 

Hexylene. 

Gaseous  Products. 


Bases. 
Ammonia, 
Methylamine, 
Ethylamine, 
Aniline, 
Quinoline, 
Picoline, 
Toluidine, 
Lutidine, 
Cumidine, 
Pyrrhol, 
Poetinine. 


Hydrogen, 
Carburetted  Hydro- 
gen, 

Bicarburetted  Hy- 
drogen, 


Various  Hydro-Car- 
bides, 
Oxide  of  Carbon, 
Sulphuret  of  Car- 
bon, 


Carbonic  Acid, 
Sulphydric  Acid, 
Hydrocyanic  Acid. 


Whatever  may  be  the  composition  of  the  dif- 
ferent kinds  of  tar,  they  are  all  submitted  to  dis- 
tillation in  order  to  isolate  the  principles  capable 
of  industrial  application.    But,  first  of  all,  it  is 


56 


DISTILLATION  OF  COAL  TAR. 


necessary  to  separate  the  tar,  as  far  as  possible, 
from  the  ammoniacal  liquor  which  is  found  with 
it.  For  this  purpose,  it  is  heated  some  hours  at 
176°  or  212°  F.,  by  which  it  is  rendered  more 
liquid,  and  then  the  water  separates  more  easily. 
It  is  then  allowed  to  cool  very  slowly,  and  the 
water  is  drawn  off  by  a  tap  placed  at  the  lower 
part  of  the  boiler.  A  certain  quantity  of  tar 
obstinately  retains  the  wTater,  constituting  a 
buttery  matter,  which  may  be  allowed  to  run 
away  wTith  the  water,  to  be  added  afterwards  to 
another  quantity  of  tar  to  be  deshydrated  by  a 
fresh  operation. 

Experience  seems  to  have  demonstrated  that 
the  most  simple  process,  that  is  to  say,  distillation 
over  a  naked  fire  at  the  ordinary  pressure,  is  still 
the  most  practicable  and  advantageous.  As  the 
volatile  products  have  but  little  latent  heat,  the 
height  of  the  still  should  be  somewhat  less  than 
the  diameter;  for  the  same  reason  the  head  must 
be  carefully  protected  from  cold,  and  it  is  well  to 
furnish  the  inside  with  a  circular  gutter,  in  which 
the  products  condensed  in  the  head  may  be  col- 
lected and  run  into  the  refrigerator.  By  this 
means  the  products  are  prevented  from  flawing 
back  into  the  boiling  tai^  and  being  decomposed 
by  coming  in  contact  with  the  sides  of  the  still, 
which,  especially  towards  the  end  of  the  operation, 
becomes  very  hot. 

In  condensing  the  vapors,  it  is  necessary  to 


DISTILLATION  OF  COAL  TAR.  57 

observe  certain  precautions.  At  the  beginning 
of  the  operation,  when  the  lighter  and  more 
volatile  oils  are  passing,  the  worm  must  be  well 
cooled  to  make  quite  sure  of  the  condensation. 
Later,  when  the  heavier  and  less  volatile  products 
are  coming  over,  the  water  in  the  refrigerator 
may  be  allowed  to  get  heated  at  86°  or  104°  F., 
and  at  last  when  the  matters  capable  of  solidi- 
fying, such  as  naphthaline  and  paraffine,  pass, 
the  temperature  of  the  refrigerator  should  never 
be  under  104°  F.,  and  it  may  be  allowed  without 
inconvenience  to  raise  to  140°  or  158°  F.  At 
this  temperature  the  products  condense  perfectly, 
but  remain  liquid  and  run  with  ease.  If  the 
refrigerator  was  kept  quite  cold  during  the  whole 
process,  it  might  happen  toward  the  end,  that  the 
condensed  tube  would  become  blocked  up  by  the 
solidified  products,  and  a  dangerous  explosion 
might  ensue. 

At  the  beginning  of  the  distillation  the  tar 
should  not  be  allowed  to  boil  too  fast.  Some  dis- 
tillers at  this  period  pass  a  current  of  steam  at 
230°  or  248°  F.,  through  the  tar  to  assist  the  dis- 
engagement of  the  more  volatile  oils. 

These,  in  condensing,  form  a  very  limpid  fluid 
liquid,  having  the  density  of  .780,  which  gradually 
rise  to  .850  ;  the  mean  (Tensity  of  all  the  products 
united  is  about  .830.  It  is  this,  which  constitutes 
the  benzine  of  commerce.  It  contains  a  great 
variety  of  compounds  whose  boiling  points  range 


58 


DISTILLATION  OF  COAL  TAR. 


from  140°  to  392°.  They  belong  to  the  following 
series : — 


O  Hn  e.  g.  Amylene,  C5  H5 

Hexylene  (oleine  Caproylene)  C6  H5 

Hepthylene  (Oenenthylene)  C7  H7 

etc. 

O  Hn  +  2  e.  g.    Propyle  C12  H14 

Butyle  C16  H  8 

Amyle  C20  H22 

etc. 

Cn  Hn— 6  e.  g.      Benzine  C12  H6 

etc. 


When  the  density  of  the  products  exceeds 
.850,  the  current  of  steam  is  stopped  and  the  heat 
increased.  As  soon  as  the  temperature  of  the  tar 
has  risen  from  392°  to  428°  R,  the  distillation  re- 
commences, and  the  oil  condensed  is  found  to  have 
a  sp.  gr.  .860  to  .900,  the  mean  being  from  .880  to 
.885.  This  product  constitutes  the  heavy  oil  of 
tar,  and  contains  phenol,  creasote,  and  aniline. 

Lastly,  the  ultimate  products  of  the  distillation, 
which  on  cooling  become  a  buttery  mass,  or  crys- 
talline, if  they  contain  much  naphthaline,  are 
set  aside  for  the  preparation  of  paraffine.  They 
are  placed  in  vats,  which  are  cooled,  in  order  that 
the  solid  matters  may  separate  by  crystallization. 

2000  parts  of  rough  oil  of  tar  obtained  by  the 
distillation  of  Boghead  coal  furnished  on  rectifi- 
cation : — 


DISTILLATION  OF  COAL  TAR.  59 


1208  parts  light  oil,  density  =  .825 
200    "     heavy  oil  =     .       .  .860 
400    "  pitch 
192    "     gas  escaped 

2900  parts  of  tar  from  gas  works  using  Boghead 
coal,  distilled  in  a  similar  manner,  yielded : — 

Water,  slightly  aminoniacal  .  .  .  .168 
Light  hydro-carbons,  mean  density  .820  .  .  480 
Heavy  hydro- carbons,  mean  density,  .863  .  883 
Fatty  pitch,  solid  when  cold,  liquid  at  302°  F.  1195 
Loss  6  per  cent  174 


2900 


60 


HISTORY  OF  ANILINE. 


CHAPTER  VIII. 

HISTORY  OF  ANILINE — PROPERTIES  OF  ANILINE — 
PREPARATION  OF  ANILINE •  DIRECTLY  FROM  COAL 
TAR. 

§  1.  History  of  Aniline. 

Aniline  was  discovered  in  1826  by  Unverdor- 
ben.  The  original  method  for  its  preparation  was 
by  digesting  indigo  with  hydrate  of  potash,  and 
subjecting  the  resulting  product  to  distillation. 
Aniline  was  also  obtained  from  the  basic  oils  of 
coal  tar;  but  the  process  which  is  now  employed 
for  its  preparation  is  a  remarkable  instance  of  the 
manner  in  which  abstract  scientific  research  be- 
comes, in  the  course  of  time,  of  the  most  import- 
ant practical  service.  It  was  Faraday  who  first. dis- 
covered benzole;  he  found  it  in^>il-gas.  After  this 
it  was  obtained  by  distilling  benzoic  acid  with 
baryta,  which  result  determined  its  formula,  and 
was  the  cause  of  its  being  called  benzole.  After 
this,  Mansfield  found  it  to  exist  in  large  quantities 
in  common  coal  tar  naphtha,  which  is  the  source 
from  which  it  is  now  obtained  in  very  large  quan- 
tities. Benzole,  when  studied  in  the  laboratory, 
was  found  to  yield,  under  the  influence  of  nitric 


HISTORY  OF  ANILINE. 


61 


acid,  nitro-benzole.  Zinin  afterwards  discovered 
the  remarkable  reaction  which  sulphide  of  ammo- 
nium exerts  upon  nitro-benzole,  converting  it  into 
aniline.  And,  lastly,  Bechamp  found  that  nitro- 
benzole  was  converted  into  aniline  when  submit- 
ted to  the  action  of  ferrous  acetate.  It  is  Be- 
champ's  process  which  is  now  employed  for  the 
preparation  of  aniline  by  the  tun.  Had  it  not 
been  for  the  investigations  briefly  cited  above,  the 
beautiful  aniline  colors  now  so  extensively  em- 
ployed, would  still  remain  unknown.  When  Mr. 
Perkins  discovered  aniline  purple,  nitro-benzole 
and  aniline  were  only  to  be  met  with  in  the  labo- 
ratory ;  in  fact,  half  a  pound  of  aniline  was  then 
esteemed  quite  a  treasure,  and  it  was  not  until  a 
great  deal  of  time  and  money  had  been  expended 
that  he  succeeded  in  obtaining  this  substance  in 
large  quantities,  and  at  a  price  sufficiently  low  for 
commercial  purposes. 

The  coloring  matters  obtained  from  aniline  are 
numerous;  they  are  the  following:  Aniline  purple, 
violine,  roseine,  futschine,  alpha  aniline  purple, 
bleu  de  Paris,  nitroso-phenyline  dinitraniline,  and 
nitro-phenyline  diamine. 

§  2.  Chemical  Properties  of  Aniline. 

Pure  aniline  is  a  colorless  liquid,  very  astrin- 
gent, having  an  aromatic  odor  and  an  acid  burning 
taste,  slightly  soluble  in  water,  very  soluble  in 
alcohol  and  ether. 

6 


62 


HISTORY  OF  ANILINE. 


Its  specific  gravity  =1.028.  It  does  not  freeze 
at  —20. 

It  boils  at  262°.4  F.,  and  distils  unchanged. 
When  warmed  it  dissolves  sulphur  and  phosphorus. 

It  is  a  powerful  basis,  combining  with  acids, 
and  forming  salts,  which  in  general  are  soluble. 

It  decomposes  salts  of  protoxide  and  peroxide 
of  iron,  and  the  salts  of  zinc  and  alumina,  preci- 
pitating from  them  the  metallic  oxides. 

It  precipitates  also  the  chlorides  of  mercury, 
platinum,  gold,  and  palladium,  but  does  not  pre- 
cipitate the  nitrates  of  mercury  and  silver. 

Aniline  easily  oxidizes,  turning  yellow  in  water, 
and  in  time  becoming  resinified. 

When  aniline  dissolved  in  hydrochloric  acid  is 
acted  on  by  chlorine,  the  solution  takes  a  violet- 
color,  and  on  continuing  the  current  of  chlorine, 
the  liquid  becomes  turbid  and  deposits  a  brown- 
colored  resinoid  mass.  In  distilling  the  whole, 
vapors  of  trichlor aniline  and  trichlorophenic  acid 
pass  over. 

A  solution  of  the  alkaline  hypochlorites  colors 
aniline  violet  blue,  which  turns  rapidly  red,  espe- 
cially in  contact  with  acids. 

A  mixture  of  hydrochloric  acid  and  chlorate  of 
potash  acts  on  aniline,  the  final  result  of  the  action 
being  chloranile  C12  CI4  O4,  but  in  the  course  of  the 
reaction  several  colored  intermediary  bodies  are 
formed. 

If  a  solution  of  chlorate  of  potash  in  hydro- 


HISTORY  OF  ANILINE. 


63 


chloric  acid  be  added  to  a  solution  of  a  salt  of 
aniline  mixed  with  an  equal  volume  of  alcohol, 
and  care  is  taken  to  avoid  an  excess  of  the  hydro- 
chloric solution,  a  flocculent  precipitate  is  deposited 
after  a  time  of  a  beautiful  indigo  blue  color;  this 
precipitate  filtered  and  washed  with  alcohol  con- 
tracts strongly,  and  passes  to  a  deep  green.  The 
filtered  liquid  has  a  brownish  red  color ;  on  boil- 
ing it,  adding  fresh  quantities  of  hydrochloric 
acid  and  chlorate  of  potash,  a  yellow  liquor  is 
obtained,  which  deposits  crystallized  scales  of 
chlor  anile. 

An  aqueous  solution  of  chromic  acid  gives,  with 
solutions  of  aniline,  a  green,  blue,  or  black  pre- 
cipitate, according  to  the  concentration  of  the 
liquors. 

When  a  small  quantity  of  an  aniline  salt  is 
mixed  in  a  porcelain  dish  with  a  few  drops  of 
strong  sulphuric  acid,  and  a  drop  of  a  solution  of 
bichromate  of  potash  is  allowed  to  fall  on  the 
mixture,  a  beautiful  blue  color  appears  after  some 
minutes,  which,  however,  soon  disappears. 

Diluted  nitric  acid  combines  with  aniline  with- 
out adhering  to  it  immediately;  but  after  some 
time  nitrate  of  aniline  crystallizes  in  the  form  of 
concentric  needles,  the  mother  liquor  turns  red 
colored,  and  the  sides  of  the  evaporating  dish 
become  covered  with  a  beautiful  blue  effer- 
vescence. When  a  few  drops  of  strong  nitric  acid 
are  poured  upon  aniline,  it  is  immediately  colored 


64 


HISTORY  OF  ANILINE. 


a  deep  blue;  on  applying  heat  the  blue  tint  quickly 
passes  to  yellow,  a  lively  reaction  is  manifested, 
which  results  in  the  formation  of  picric  acid,  or 
trinitrophenisic  acid. 

Potassium  dissolves  in  aniline,  disengaging 
hydrogen,  whilst  all  becomes  a  velvet-colored  pap. 

The  other  reactions  of  aniline  which  are  cha- 
racterized by  the  formation  of  Futschine  Aza- 
leine,  will  be  related  in  the  sequel  of  this  book, 
when  describing  their  preparations. 

§  3.  Preparation  of  Aniline  directly  from  Coal  Tar. 

The  method  which  appears  to  be  the  most  ra- 
tional, and  which  deserves  to  be  tried,  would  consist 
in  treating  the  tar  as  condensed  in  gas  works  with 
hydrochloric  or  sulphuric  acid,  diluted  with  three 
or  four  times  its  volume  of  water.  Mechanical 
means  for  affecting  the  intimate  mixture  of  the 
tar  with  the  acid  might  be  easily  contrived,  but 
in  the  absence  of  any  special  contrivance,  the  end 
may  be  obtained  by  half  filling  a  barrel  with  the 
tar,  adding  one-fifth  or  one-sixth  of  its  volume  of 
acid,  and  rolling  and  shaking  the  barrel  until  the 
acid  has  taken  up  the  bodies  with  which  it  is  able 
to  combine;  the  whole  might  thus  be  run  into  a 
cistern,  where,  by  degrees," the  watery  liquid  would 
separate  from  the  tar. 

The  same  acid  liquid  might  be  used  over  and 
over  again  until  the  bases  have  nearly  saturated 
the  acid.   A  very  impure  aqueous  solution  would 


HISTORY  OF  ANILINE. 


65 


thus  be  obtained,  containing  the  hydrochlorates 
or  sulphates  of  ammonia,  and  all  the  other  organic 
bases  contained  in  the  tar,  such  as  aniline,  quino- 
line,  pyrrol,  picoline,  pyrrhidine,  lutidine,  toluidine, 
cumidine,  etc. 

By  evaporating  this  solution  almost  to  dryness, 
and  then  distilling  with  an  excess  of  milk  of  lime, 
the  bases  would  be  set  at  liberty.  Ammonia,  as 
the  most  volatile,  would  be  disengaged  first,  and 
might  be  condensed  apart,  and  by  raising  the  tem- 
perature higher  and  higher,  the  organic  bases 
would  be  disengaged.  Aniline  would  be  found 
among  the  liquids  distilling  between  302°  and 
482°  F. 

The  manipulation  of  the  tar,  however,  is  an 
extremely  disagreeable  operation,  and  presents 
many  difficulties;  it  is  therefore  preferable,  in 
many  cases,  to  distil  the  tar  first,  and  operate  on 
the  most  pure  and  limpid  distilled  oil. 

Aniline,  because  of  its  high  boiling  point,  is 
never  met  with,  in  the  light  and  volatile  liquids 
when  first  distilled  from  tar.  The  most  of  it  is 
found  in  those  which  distil  between  302  and  356.° 
These,  according  to  Hoffmann,  contain  about  10 
per  cent,  of  organic  bases,  mostly  aniline  and  qaino- 
line.  The  oils  which  distil  above  482°,  contain 
mostly  quinoline  and  very  little  aniline. 

The  following  process  for  extracting  the  two 
bases  from  the  oil  and  separating  them,  is  due  to 
Hoffmann.   The  oil  is  agitated  strongly  with  com- 

6* 


66 


HISTORY  OF  ANILINE. 


mercial  hydrochloric  acid.  The  mixture  is  then 
allowed  to  rest  for  12  or  14  hours,  and  the  oil  is 
separated  from  the  acid ;  the  latter  is  treated  again 
by  fresh  quantities  of  oil  until  nearly  saturated. 
The  still  acid  solution  is  filtered  to  retain  the  oil 
interposed  mechanically.  It  is  then  placed  in  a 
copper  still  and  supersaturated  with  an  excess  of 
milk  of  lime.  At  the  moment  of  saturation  an 
abundance  of  vapors  are  given  off,  and  the  head 
must  be  quickly  fixed  on  the  still.  Heat  is  now 
applied  so  as  to  obtain  a  quick  and  regular  ebulli- 
tion. 

The*  condensed  product  is  a  milky  liquid  with 
oily  drops  floating  on  it.  The  distillation  is  car- 
ried on,  as  long  as  the  vapor  has  the  peculiar  odor 
of  the  first  part  distilled,  or  the  condensed  product 
gives  the  characteristic  reaction  of  aniline  with 
chloride  of  lime. 

The  milky  liquid  is  now  saturated  with  hydro- 
chloric acid ;  it  is  then  concentrated  in  a  water 
bath  ;  and  lastly,  decomposed  in  a  tall  narrow  ves- 
sel by  means  of  a  slight  excess  of  hydrate  of  pot- 
ash or  soda.  The  bases  set  free,  unite  and  form 
an  oily  liquid,  which  floats  on  the  alkaline  solu- 
tion. This  is  removed  with  a  pipette  and  rectified. 
The  rectified  product  is  aniline,  sufficiently  pure 
for  industrial  purposes,  especially  if  we  set  aside 
the  part  distilling  above  392°  or  428°  F.,  which  is 
principally  composed  of  quinoline. 

To  obtain  aniline  chemically  pure,  the  neutral 


.    HISTORY  OF  ANILINE. 


67 


oils  forming  part  of  the  oily  layer  must  be  com- 
pletely removed.  This  is  done  by  dissolving  the 
whole  in  ether,  and  adding  dilute  hydrochloric 
acid,  which  combines  with  and  separates  the  bases, 
and  leaves  the  oil  in  solution  in  ether.  The  acid 
solution  is  then  decanted,  decomposed  with  pot- 
ash, and  submitted  to  careful  fractional  distillation. 
If  the  products  are  gathered  separately  in  three 
parts,  the  first  will  contain  ammonia,  water,  and 
some  aniline;  the  second  will  be  pure  aniline;  while 
the  third  portion  will  contain  mostly  quinoline. 
An  alcoholic  solution  of  oxalic  acid  is  now  added 
to  the  impure  aniline,  which  precipitates  oxalate 
of  aniline,  as  a  mass  of  white  crystals,  which  are 
washed  with  alcohol,  and  then  pressed.  The  salt 
is  then  dissolved  in  a  small  quantity  of  water,  to 
which  a  little  alcohol  is  added.  From  this  solu- 
tion, the  oxalate  crystallizes  in  stellated  groups 
of  oblique  rhomboidal  prisms.  These  crystals  are 
decomposed  by  a  caustic  alkali,  to  set  free  the 
aniline,  and  when  this  is  distilled,  water  at  first 
passes,  then  water  charged  with  aniline,  and  lastly, 
at  359°  F.,  chemically  pure  aniline. 


63 


PREPARATION  OF  ANILINE,, 


CHAPTER  IX. 

ARTIFICIAL  PREPARATION  OF  ANILINE— PREPARA- 
TION OF  BENZOLE— PROPERTIES  OF  BENZOLE — 
PREPARATION  OF  N1TRO-BENZOLE — TRANSFOR- 
MATION OF  NITRO-BENZOLE  INTO  ANILINE,  BY 
MEANS  OF  SULPHIDE  OF  AMMONIUM  ;  BY  NASCENT 
HYDROGEN;  BY  ACETATE  OF  IRON;  AND  BY 
ARSENITE  OF  POTASH — PROPERTIES  OF  THE  BI- 
NITRO-BENZOLE. 

Artificial  Preparation  of  Aniline. 

This  process  constitutes  one  of  the  most  im- 
portant and  curious  reactions  of  organic  chem- 
istry; it  enables  us  to  obtain  aniline  in  any  quan- 
tity. It  is  not  difficult  to  prepare,  but  certain 
precautions  are  however  necessary,  when  ope- 
rating on  a  large  scale.  The  process  can  be 
subdivided  into  three  distinct  operations : — 

1.  Preparation  of  benzole. 

2.  Transformation  of  benzole  into  nitro-ben- 
zole. 

3.  Reduction  of  nitro-benzole  into  aniline. 


PREPARATION  OF  BENZOLE.  69 


§  1.  Preparation  of  Benzole. 

The  only  process  we  think  necessary  to  notice 
is  that  by  which  benzole  is  obtained  on  a  large 
scale,  viz :  the  extraction  from  coal  tar,  or  from 
the  first  products  of  the  distillation  of  coal  tar, 
light  oil,  or  crude  naphtha. 

The  manufacturer  who  wishes  to  distil  tar  in 
order  to  procure  the  largest  amount  of  benzole, 
should  choose  a  light  fluid  tar,  and  especially  one 
distilled  from  boghead  or  cannel  coal.  To  form  a 
comparative  estimate  of  the  value  of  different  tars, 
the  following  experiment  may  be  performed  :— 

About  2J  gls.  of  tar  are  distilled  until  the 
vapors,  instead  of  condensing  into  a  liquid,  fur- 
nish a  product  which,  on  cooling,  becomes  solid, 
or  of  a  buttery  consistence.  By  carefully  observ- 
ing when  the  condensed  oil  becomes  heavier  than 
the  water,  and  measuring  the  volume  of  the  lighter 
oils  which  float  on  the  surface  of  the  water,  and 
then  comparing  the  volumes,  we  are  enabled  to 
estimate  with  tolerable  accuracy  the  value  of  the 
tar.  Of  course,  the  one  which  yields  the  largest 
amount  of  light  oil  is  the  best. 

Crude  naphtha,  or  the  benzole  of  commerce,  is 
generally  a  yellow  or  brown  liquid,  having  a 
density  varying  from  .90  to  .95 ;  it  usually  con- 
tains, besides  benzole,  some  of  the  homologues  of 
benzole,  toluol,  cumol,  and  cymol.  It  is  impossi- 
ble to  separate  these  bodies  by  an  ordinary  pro- 


70 


PREPARATION  OF  BENZOLE. 


cess  of  rectification  ;  for  although  the  boiling  point 
of  toluol  is  226°  or  228°,  and  that  of  cumol  289° 
or  293°,  their  vapors  are,  so  to  say,  dissolved  in 
the  vapor  of  benzole,  and  are  carried  over  and 
condensed  together.  Their  presence,  however, 
does  not  interfere  with  the  preparation  of  nitro- 
benzole  and  aniline. 

When  you  have  obtained  the  light  oil  from 
the  coal  tar,  wash  it  with  a  little  sulphuric  acid 
(10  per  cent,  of  strong  acid).  Leave  it  one  hour, 
and  saturate  with  soda. 

Distil ;  the  product  escapes  through  a  cool 
worm. 

In  the  receiver  are  two  oils,  one  lighter  and 
the  other  heavier  than  water,  the  first  occupies 
about  one-tenth  of  the  total  volume:  it  is  the 
benzole;  add  to  it  a  little  sulphuric  acid,  wash 
and  distil  it. 

The  benzole  found  in  commerce  is  sometimes 
very  impure;  some  has  been  met  with,  contain- 
ing merely  a  trace  of  real  benzole.  Such  an 
article  is  ordinarily  the  result  of  the  distillation 
of  bituminous  schists  or  asphaltum,  and  besides 
hydrocarbons  belonging  to  another  series  than 
that  of  benzole,  it  generally  contains  a  small 
amount  of  oxygenated  products,  and  consequently 
cannot  be  advantageously  used  in  the  preparation 
of  aniline. .  It  is  therefore  important  to  be  able 
to  detect  benzole  in  a  mixture  of  other  oils.  For 
this  purpose  we  may  avail  ourselves  of  the  facility 


PROPERTIES  OF  BENZOLE. 


with  which  true  benzole  is  converted  into  nitro- 
benzole,  and  then  into  aniline  by  the  action  of 
nascent  hydrogen. 

The  following  is  Hoffmann's  method :  a  drop  of 
benzole  is  heated  in  a  small  test  tube,  with  fuming 
nitric  acid,  to  convert  it  into  nitro-benzole.  A 
good  deal  of  water  is  then  added,  to  precipitate 
the  nitro-benzole  in  small  drops,  which  must  be 
taken  up  by  ether.  The  ethereal  solution  is 
then  poured  into  another  small  tube,  and  equal 
volumes  of  alcohol  and  diluted  hydrochloric  acid 
are  then  added;  a  few  fragments  of  granulated 
zinc  are  then  dropped  in.  In  about  5  minutes 
sufficient  hydrogen  will  have  been  disengaged  to 
produce  aniline,  which  will  be  found  combined 
with  the  acid.  The  liquid  is  supersaturated  with 
an  alkali  and  shaken  with  ether,  which  dissolves 
the  aniline  set  free.  A  drop  of  this  ethereal  solu- 
tion allowed  to  evaporate  in  a  watch  glass,  and 
mixed  after  the  evaporation  of  the  ether  with  a 
drop  of  a  solution  of  hypochlorite  of  lime,  will 
show  the  violet  tints  which  characterize  aniline. 
The  operations  may  be  executed  rapidly,  ^and 
without  any  difficulty. 

Properties  of  Benzole. 

At  the  ordinary  temperature,  benzole  is  in  the 
form  of  a  colorless,  very  fluid  liquid,  of  an  agree- 
able odor,  and  has,  a  specific  gravity  of  .85  at 


72  PROPERTIES  OF  BENZOLE. 


59°  F.  At  a  very  low  temperature  it  crystallizes  or 
forms  a  mass  like  camphor,  which  melts  at  41°. 

Its  boiling  point  is  between  176°  and  170°.8 ; 
and  it  distils  without  undergoing  any  change.  It 
is  nearly  insoluble  in  water,  to  which  it  imparts 
its  peculiar  odor;  it  is  very  soluble  in  alcohol, 
ether,  wood  spirit,  the  essential  and  fatty  oils ;  it 
easily  dissolves  camphor,  wax,  fatty  matters,  India 
rubber,  gutta  percha,  and  a  great  number  of  resins. 
Amongst  the  last  those  which  are  the  least  soluble 
in  it  are  shellac,  copal,  and  animi.  It  is  very  in- 
flammable, and  burns  with  a  smoky  flame.  Hy- 
drogen gas  passed  through  it,  and  charged  with 
its  vapor,  burns  with  a  very  clear,  luminous  flame. 

Chlorine  and  bromine  convert  benzole  into  the 
terchloride  and  terbromide  of  benzole.  To  the 
direct  solar  light,  the  change  takes  place  very 
quickly.  Concentrated  sulphuric  acid  dissolves 
benzole,  and  when  the  mixture  is  gently  heated  a 
copulated  acid,  sulpho-henzolic  acid,  is  formed,  C12, 
H6,S2,06,  the  hydrogen  of  which  may  be  replaced 
by  metals.  As  this  acid  is  soluble  in  water,  in 
purifying  rough  benzole  with  sulphuric  acid,  it  is 
necessary  to  avoid  using  an  excess  of  the  acid, 
and  also  heating  the  mixture.  A  solution  of 
chromic  acid  does  not  act  on  benzole,  and  is  there- 
fore a  good  agent  for  the  purification.  Concen- 
trated nitric  acid  converts  benzole  into  nitro- 
benzole,  to  the  manufacture  of  which  we  proceed. 


PREPARATION  OF  NITRO-BENZOLE.  73 


Preparation  of  Nitro-Benzole. 

The  preparation  of  nitro-benzole  is  accom- 
plished on  a  large  scale,  by  allowing  a  fine  stream 
of  benzole,  and  another  of  the  strongest  nitric 
acid,  to  run  together  in  a  worm  or  long  glass  tube 
kept  well  cooled.  The  two  liquids  react  on  each 
other  on  coming  in  contact,  heat  is  disengaged, 
and  nitro-benzole  is  formed. 

Commercial  nitric  acid,  mixed  with  half  its 
volume  of  sulphuric  acid,  may  be  substituted  for 
the  concentrated  nitric  acid. 

The  nitro-benzole  collected  at  the  end  of  the 
worm,  is  first  washed  with  water,  then  with  a 
solution  of  carbonate  of  soda,  and  afterwards  once 
more  with  water. 

Properties  of  Nitro  and  Bi-Nitro-Benzole— 
Nitro-Benzole. 

Nitro-benzole  is  a  yellowish  liquid,  which,  at 
59°  R,  has  a  specific  gravity  of  1.209.  It  boils 
at  415°,  4  F.,  and  cools  at  37°,  4;  it  crystallizes  in 
needles.  Having  an  odor  closely  resembling  that 
of  the  bitter  almond,  it  has  been  largely  used  in 
perfumery  for  scenting  fancy  soaps,  for  which 
purpose  it  has  one  advantage  over  the  oil  of  bitter 
almonds-— it  is  less  affected  by  the  action  of  alka- 
lies. Almost  insoluble  in  water,  it  is  very  soluble 
in  alcohol,  ether,  and  essential  oils. 

Concentrated  sulphuric  and  nitric  acids  dissolve 
7 


74 


BI-NITRO  BENZOLE. 


it,  but  it  is  precipitated  by  the  addition  of  water. 
It  is  decomposed  by  a  continued  boiling  with 
sulphuric  acid;  and  under  the  same  circumstances 
with  concentrated  nitric  acid,  it  forms  bi-nitro- 
benzole.  Neither  the  alkalies  in  strong  aqueous 
solution,  nor  quick  lime,  act  on  nitro-benzole ; 
but  an  alcoholic  solution  of  the  alkalies,  acts 
energetically  and  forms  azoxy-benzole  (C24,H10,N2, 
O2).  By  the  action  of  nitric  acid  on  this  last 
substance  a  number  of  other  interesting  bodies  are 
produced,  which  it  is  not  necessary  to  describe 
here. 

Bi-Nitro-Benzo  le. 

Bi-nitro-benzole  is  formed  when  nitro-benzole 
is  added,  drop  by  drop,  to  a  mixture  of  equal  parts 
of  fuming  nitric  acid  and  sulphuric  acid,  as  long 
as  the  liquids  will  mix.  If  such  a  mixture  be 
boiled  for  a  few  minutes;  it  becomes,  on  cooling, 
a  thick  magma  of  bi-nitro-benzole,  which  is  easily 
purified  by  repeated  washings  with  water.  A 
single  crystallization  from  alcohol  will  furnish 
this  body  in  long  brilliant  prisms  which  melt  at  a 
temperature  above  212°,  and  crystallize  again  on 
cooling  in  a  radiated  mass. 

Bi-nitro-benzole  is  very  soluble  in  warm  alco- 
hol. When  a  plate  of  zinc,  well  cleaned,  is  placed 
in  a  cold  alcoholic  solution  of  bi-nitro-benzole,  and 
hydrochloric  acid  is  added  by  degrees,  we  observe 
that  the  disengagement  of  hydrogen,  which  at  first 


BI-NITRO-BENZOLE; 


75 


takes  place;  soon  ceases,  and'  at  the  same  time  the 
liquid  takes  a  crimson  red  tint.*  The  reaction 
being  completed,  the  excess  of  zinc  is  removed 
and  the  liquor  is  saturated  by  an  alkali,  which 
precipitates  the  oxide  of  zinc  colored  in  deep  pur- 
ple. The  precipitate  is  collected  on  a  filter  and 
washed  with  alcohol. 

By  distilling  the  highly  colored  alcoholic  wash- 
ings, washing  the  residue  with  cold  water,  then 
re-dissolving  it  in  alcohol  and  evaporating  it  afresh 
to  dryness,  the  new  matter  is  obtained  perfectly 
pure,  ^he  authors  have  given  it  the  name  of 
Nitrosophenyline,  C12  H6  N2  O2.  When  obtained  as 
above,  it  is  a  black  shining  substance;  when 
heated,  it  fuses  and  decomposes  directly;  it  is 
almost  insoluble  in  water,  but  freely  soluble  in 
alcohol  and  acids.  An  alcoholic  solution  contain- 
#  ing  only  0.2  per  cent,  is  so  deeply  colored  that  by 
reflected  light  the  solution  seems  opaque  and  of 
an  orange  red. 

Concentrated  hydrochloric  and  diluted  sulphuric 
and  nitric  acids  form  magnificent  crimson  red  solu- 
tions with  nitrosophenyline,  which  is  precipitated 
from  them  again  unchanged  by  alkalies. 

Bi-nitro-benzole  treated  with  an  alcoholic  solu- 
tion of  sulphide  of  ammonium,  is  at  first  converted 
into  nitro-aniline. 

C12  H6  (NO)4  N=.C12  H6  N2  O4, 

*  Cliurcli  &  Perkins.    Quart.  Journ.  Chem.  Soc,  ix.  p.  1. 


76 


BI-NITR0-BENZ0LE. 


that  is  to  say,  aniline,  in  which  one  equivalent  of 
hydrogen  is  replaced  by  one  of  nitrous  vapor. 
Nitro-aqjline  crystallizes  in  yellow  needles,  which 
stain  the  epidermis  like  picric  acid. 

Transformation  of  Nitro- Benzole  into  Aniline. 

(a).  By  means  of  Sulphide  of  Amm.onium. — An 
alcoholic  solution  of  nitro-benzole,  after  having 
been  saturated  with  ammoniacal  gas,  is  treated 
with  a  current  of  sulphuretted  hydrogen.  The 
liquor  now  becomes  of  a  deep  dirty  green  color, 
and  deposits  a  little  sulphur.  It  is  now  left^ twenty- 
four  hours,  during  which  time  crystals  of  sulphur 
are  deposited,  the  odor  of  sulphuretted  hydrogen 
disappears,  and  is  replaced  by  a  strong  ammoniacal 
smell.  If  distilled  now  to  recover  the  alcohol,  a 
good  deal  of  sulphur  is  deposited,  and  it  is  impos- 
sible to  continue  the  distillation  long,  on  account 
of  the  violent  bumping  which  ensues.  It  is,  there- 
fore, allowed  to  cool,  and  the  sulphur  is  removed. 
On  distilling  the  liquor  again,  more  sulphur  is 
deposited,  which  must  also  be  removed.  The 
process  must  be  continued,  re-saturating  the  liquor 
with  sulphuretted  hydrogen  if  need  be,  until  a 
heavy  oily  matter  (aniline)  deposits,  which  must 
be  separated  from  the  liquor  and  re-distilled  by 
itself.    The  aniline  is  thus  obtained  nearly  pure. 

Instead  of  using  an  alcoholic  solution  of  nitro- 
benzole,  and  treating  it  successively  with  ammonia 
and  sulphuretted  hydrogen,  the  alcoholic  solution 


REDUCTION  OF  NITRO-BENZOLE.  77 


of  sulphide  of  ammonium  may  be  prepared  before- 
hand, and  the  nitro-benzole  poured  into  it.  A 
part  is  dissolved  immediately,  and  the  remainder 
by  dryness  in  the  course  of  the  operation.  It  is 
sometimes  advantageous,  instead  of  waiting  until 
the  aniline  separates,  to  add  hydrochloric  acid  to 
the  liquor  in  the  retort  until  it  is  slightly  acid, 
and  then  to  distil  almost  to  dryness,  by  which 
means  chloride  of  aniline  is  obtained.  This  is 
decomposed  by  an  excess  of  caustic  soda,  and  the 
aniline  set  at  liberty,  is  distilled  off. 

To  avoid  any  danger  from  the  bumping,  a  tinned 
copper  still  must  be  used,  which  should  be  heated 
by  steam  under  a  high  pressure ;  at  first  the  tem- 
perature should  not  exceed  162°  F.,  but  after  some 
time  it  could  be  raised  to  212°  or  230°  P. 

The  arnmoniacal  alcohol  condensed  in  the  worm 
may  be  re-saturated  with  sulphuretted  hydrogen, 
and  used  over  again  with  a  new  quantity  of  nitro- 
benzole. 

(b).  Reduction  of  Nitro- Benzole  by  Nascent  Hydro- 
gen.— In  preparing  aniline  by  this  process,  the 
nitro-benzole  and  zinc  are  placed  in  a  vessel,  and 
diluted  hydrochloric  or  sulphuric  acid  is  added 
so  as  to  produce  the  disengagement  of  a  small 
quantity  of  hydrogen.  By  degrees  the  nitro-ben- 
zole disappears,  and  aniline  is  formed,  which  re- 
mains in  solution  in  hydrochloric  or  sulphuric 
acid. 

if  * 


78  REDUCTION  OF  NITRO-BENZOLE. 


To  isolate  it,  an  excess  of  caustic  soda  is  added 
and  the  mixture  is  distilled;  the  aniline  passes  over 
with  the  vapor  of  water. 

Beauchamp  first  recommended  the  employment 
of  acetic  acid  and  iron  filings.  He  places  in  a  re- 
tort 1  lb.  of  nitro-benzole,  1J  lb.  of  iron  filings,  1 
lb.  of  concentrated  acetic  acid.  The  reaction  takes 
place  without  the  application  of  external  heat,  the 
mixture  becoming  hot  by  itself,  and  the  vapor 
being  condensed  in  a  receiver  which  must  be  kept 
well  cooled.  The  condensed  products  consist  of 
aniline,  acetate  of  aniline,  and  some  unchanged 
nitro-benzole.  These  are  allowed  to  cool,  and  are 
then  returned  to  the  retort  and  again  distilled  to 
dryness. 

The  distillate  is  now  treated  with  fused  caustic 
potash,  and  the  aniline  separates  as  an  oily  layer, 
which  must  be  removed  and  distilled  once  more. 

The  residue  of  the  mixture  of  iron  filings,  acetic 
acid  and  nitro-benzole,  which  remains  in  the  re- 
tort after  the  distillation,  still  contains  a  consider- 
able amount  of- aniline;  to  obtain  this,  the  retort 
must  be  washed  out  with  water  acidulated  with 
sulphuric  or  hydrochloric  acid,  and  the  solution 
filtered,  and  then  evaporated  to  dryness. 

The  dry  residue  is  then  mixed  with  quick  lime 
and  placed  in  an  iron  or  refractory  ware  retort, 
and  distilled,  and  the  aniline  thus  obtained  must 
be  rectified. 


REDUCTION  OF  NITKO- BENZOLE,  ETC.  79 

(c).  Reduction  of  Nitro- Benzole  by  Acetate  of  Iron. 
— Acetate  of  iron  reacts  on  nitro-benzole  and  con- 
verts it  into  aniline,  while  the  sulphate,  chloride 
and  oxalate  of  iron,  have  no  action  on  it.  The 
reaction  is  represented  thus, 

C12  II5  AzO4  +  12FeO  +  2HO  +  A= 

Nitro  Benzole     +        Acetate  of  Iron, 

C'2  H7  Az     +  _  A  

Aniline     +       Acetic  Acid. 

One  part  of  nitro-benzole  is  placed  in  a  retort 
with  an  aqueous  solution  of  acetate  of  iron,  the 
retort  is  then  heated  over  a  water  bath  for  several 
hours,  and  then  the  contents  are  filtered,  being 
dilated  with  water  if  they  have  become  pasty. 

The  residue  left  on  the  filter,  which  is  princi- 
pally peroxide  of  iron,  is  washed  with  boiling 
water.  The  filtrate  and  washings  are  then  dis- 
tilled. The  condensed  products  being  wTater, 
acetic  acid,  and  acetate  of  aniline.  These  may  be 
again  distilled  with  strong  sulphuric  acid,  using 
4-10  the  weight  of  the  nitro-benzole  employed  to 
recover  the  acetic  acid,  and  form  sulphate  of 
aniline,  and  the  latter  may  be  decomposed  by 
caustic  potash  and  the  aniline  distilled  off.  This 
process  has  not  been  found  advantageous,  and  has 
consequently  been  given  up. 


80 


REDUCTION  OF  NITRO-BENZOLE,  ETC. 


(d).  Reduction  of  Nitro -Benzole  hy  Means  of  Arse- 
nite  of  Potash  or  Soda. — In  this  process  digest 
nitro-benzole  with  a  solution  of  arsenious  acid  in 
a  strong  lye  of  caustic  soda  or  potash,  or  place  the 
arsenical  solution  in  a  tubulated  retort,  heat  it  to 
the  boiling  point,  and  then  allow  the  nitro-benzole 
to  fall  drop  by  drop  in  it.  Under  these  circum- 
stances, nitro-benzole  is  transformed  into  aniline, 
which  distils  over,  and  it  is  only  necessary  to 
saturate  with  an  alcoholic  solution  of  oxalic  acid 
to  obtain  perfectly  pure  oxalate  of  aniline. 


ANILINE  PURPLE. 


81 


CHAPTER  X. 


ANILINE    PURPLE  —  VIOLINE — ROSEINE— EMERAL- 
DINE — BLEU  DE  PARIS. 


It  has  been  known  for  many  years  that  hypo- 
chlorites react  on  aniline  and  its  salts,  producing 
a  purple-colored  solution;  in  fact,  hypochlorites 
are  the  distinguishing  test  for  aniline ;  but  nothing 
definite  was  known  of  this  purple-colored  solu- 
tion, it  being  simply  stated  that  aniline  produced 
with  hypochlorites  a  purple-colored  liquid,  but 
that  this  color  was  very  fugitive.  Many  absurd 
statements  have  been  made  respecting  the  dis- 
covery of  aniline  purple.  We  will  just  briefly 
mention  how  it  was  discovered  by  Mr.  Perkins. 

In  the  early  part  of  1856,  he  commenced  an 
investigation  on  the  artificial  formation  of  quinia. 
To  obtain  this  basis,  he  proposes  to  act  on  tolui- 
dine  with  iodide  of  allyle,  so  as  to  form  allyle 
toluidine,  which  has  the  formula: — 


§  1.  Aniline  Purple. 


V,  H7, 
C3,  H5, 
H, 


*  82 


ANILINE  PURPLE. 


thinking  it  not  improbable  that  by  oxidizing 
this,  he  might  obtain  the  desired  result  thus: — 
2  (C10  H13  N)  +  03*=  C20  II24  N2  O2  +H2  0. 

Allyle-toluidine.  Quinia. 

For  this  purpose  he  mixed  the  neutral  sulphate 
of  allyle  toluidine  with  bichromate  of  potash  ;  but 
instead  of  quinia  he  obtained  a  dirty  reddish- 
brown  precipitate.  Nevertheless,  being  anxious 
to  know  more  about  this  curious  reaction,  he  pro- 
ceeded to  examine  a  more  simple  base  under  the 
same  circumstances.  For  this  purpose  he  selected 
aniline,  and  treated  its  sulphate  with  bichromate 
of  potash.  This  mixture  produced  nothing  but  a 
very  unpromising  black  precipitate,  but  on  in- 
vestigating this  precipitate  he  found  it  to  contain 
the  substance  which  is  now,  we  may  say,  a  com- 
mercial necessity,  namely,  aniline  purple. 

The  method  adopted  for  the  preparation  of 
aniline  purple  is  as  follows:  Solutions  of  equiva- 
lent proportions  of  sulphate  of  aniline  and  bi- 
chromate of  potash  are  mixed,  and  allowed  to 
stand  till  the  reaction  is  complete.  The  resulting 
black  precipitate  is  then  thrown  on  a  filter,  and 
washed  with  water  until  free  from  sulphate  of 
potash.  It  is  then  dried.  This  dry  product  is 
afterwards  digested  several  times  with  coal-tar 
naphtha  until  all  resinous  matter  is  separated, 
and  the  naphtha  ceases  to  be  colored  brown. 
After  this  it  is  repeatedly  boiled  with  alcohol  to 


ANILINE  PUKPLE. 


83 


extract  the  coloring  matter.  This  alcoholic  solu- 
tion, when  distilled,  leaves  the  coloring  matter  in 
the  bottom  of  the  retort  as  a  beautiful  bronze- 
colored  substance. 

The  aniline  purple  prepared  according  to  the 
process  just  described;  although  suitable  for  prac- 
tical purposes,  is  not  chemically  pure.  If  re- 
quired pure,  it  is  best  to  boil  it  in  a  large  quan- 
tity of  water,  then  filter  the  resulting  colored 
solution,  and  precipitate  the  coloring  matter  from 
it  by  means  of  an  alkali.  The  precipitate  thus 
obtained  should  be  collected  on  a  filter,  washed 
with  water  until  free  from  alkali,  and  dried. 
When  dry  it  is  to  be  dissolved  in  absolute  alcohol, 
the  resulting  solution  filtered,  and  then  evapo- 
rated to  dryness  over  the  water-bath.  Thus 
obtained,  aniline  purple  appears  as  a  brittle  sub- 
stance, having  a  beautiful  bronze-colored  surface ; 
but  if  some  of  its  alcoholic  solution  be  evaporated 
on  a  glass  plate,  and  viewed  by  transmitted  light, 
it  appears  a  beautiful  bluish  violet  color.  If 
considerable  quantities  of  an  alcoholic  solution  of 
the  coloring  matter,  containing  a  little  water,  be 
evaporated  to  dryness,  the  surface  of  the  coloring 
matter  next  to  the  evaporating  dish  when  detached, 
often  possesses  a  golden  green  appearance.  Ani- 
line purple  is,  with  difficulty,  soluble  in  cold 
water,  although  it  imparts  a  deep  purple  color  to 
that  liquid.  It  is  more  soluble  in  hot  water,  but 
its  hot  aqueous  solution  when  left  to  cool  assumes 


84 


ANILINE  rUKPLE. 


the  form  of  a  purple  jelly.  It  is  very  soluble  in 
alcohol,  though  nearly  insoluble  in  ether  and 
hydrocarbons.  Aniline  dissolves  it  readily.  In 
properties,  it  seems  to  be  slightly  basic,  as  it  is 
more  soluble  in  acidulated  than  in  pure  water. 
Alkalies  and  saline  substances  precipitate  it  from 
its  aqueous  solution,  as  a  dark  purplish-black 
powder.  Bichloride  of  mercury  precipitates  it 
in  a  very  finely  divided  state ;  a  little  of  this  pre- 
cipitate, which  appears  to  be  a  double  compound 
of  chloride  of  mercury  and  coloring  matter,  when 
suspended  in  water  and  viewed  by  transmitted 
light;  appears  of  a  blue  or  violet  color.  If  a  small 
quantity  of  hydrates  of  potash  or  soda  be  added  to 
an  alcoholic  solution  of  the  coloring  matter,  it 
causes  it  to  assume  a  violet  tint,  but  without 
effecting  any  change  in  the  coloring  matter  itself. 
Ebullition  with  alcoholic  potash  does  not  decom- 
pose it.  Aniline  purple  dissolves  in  concentrated 
sulphuric  acid,  forming  a  dirty  green  solution. 
This,  when  slightly  diluted,  assumes  a  beautiful 
blue  color.  Excess  of  water  restores  it  to  its 
original  purple  color.  We  have  had  a  specimen 
of  this  coloring  matter  heated  for  an  hour  to  100° 
Centigrade  with  Nordhausen  sulphuric  acid,  with- 
out suffering  decomposition,  being  restored  to  its 
original  color  by  means  of  water,  and  possessing 
precisely  the  same  properties  as  it  had  before 
being  subjected  to  this  powerful  agent.  Hydro- 
chloric acid  acts  upon  it  in  the  same  manner  as 


ANILINE  PURPLE. 


85 


sulphuric  acid.  It  is  decomposed  by  chlorine, 
and  also  by  fuming  nitric  acid.  Bichloride  of  tin 
is  without  action  upon  it.  Powerful  reducing 
agents  have  a  peculiar  action  upon  this  coloring 
matter,  somewhat  analogous  to  the  action  of  re- 
ducing agents  on  indigo.  An  alcoholic  solution 
of  the  coloring  matter  when  mixed  with  a  little 
protoxide  of  iron  changes  to  a  pale  brown  color. 
This  solution  also  becomes  purple  when  exposed 
to  the  action  of  the  atmosphere.  Sulphurous 
acid  does  not  affect  the  color  of  this  substance. 

This  coloring  matter  forms  a  remarkable  com- 
pound with  tannin.  When  an  aqueous  solution 
of  the  coloring  matter  is  mixed  with  a  solution  of 
tannin,  precipitation  takes  place;  the  precipitate 
thus  formed,  after  having  been  well  washed,  no 
longer  possesses  the  properties  of  the  pure  color- 
ing matter.  It  is  insoluble  in  water.  Like  the 
pure  coloring  matter,  it  dissolves  in  concentrated 
sulphuric  acid,  forming  a  dirty  green  liquid,  but 
on  adding  an  excess  of  water  to  that  solution,  the 
new  compound  is  precipitated  unchanged.  This 
compound  is  rather  duller  in  color  than  the  pure 
coloring  matter  itself.  Aniline  purple,  when 
agitated  with  a  little  moist  binoxide  of  lead,  is 
transformed  into  Eoseine.  Its  coloring  matter  is 
remarkable  for  its  intensity;  a  few  grains  will 
color  a  considerable  quantity  of  spirit  of  wine. 


8 


86 


VIOLINE. 


§  2.  Violine. 

This  coloring  matter,  which  is  a  product  of  the 
oxidation  of  aniline,  was  first  obtained  by  Dr. 
David  Price.  He  prepares  it  by  heating  an  aqueous 
liquid,  containing  two  equivalents  of  sulphuric 
acid  and  one  equivalent  of  aniline,  to  the  boiling 
point,  and  then  adding  one  equivalent  of  binoxide 
of  lead,  boiling  the  mixture  for  some  time  and 
filtering  it  whilst  hot.  The  filtrate,  which  is  of  a 
dark  purple  hue,  is  boiled  with  potash,  to  separate 
the  excess  of  aniline,  and  also  to  precipitate  the 
coloring  matter.  When  all  the  free  aniline  is 
volatilized,  the  residue  is  thrown  on  a  filter  and 
slightly  washed  with  water,  and  then  dissolved  in 
a  dilute  solution  of  tartaric  acid.  This  solution, 
after  filtration,  is  evaporated  to  a  small  bulk,  re- 
filtered,  and  then  precipitated  by  means  of  an 
alkali.  Thus  obtained,  violine  presents  itself  as  a 
blackish  purple  powder,  which,  when  dissolved  in 
alcohol  and  evaporated  to  dryness,  appears  as  a 
brittle,  bronze-colored  substance,  similar  to  aniline 
purple,  but  possessing  a  more  coppery  colored 
reflection.  It  is  more  insoluble  in  water  than  the 
preceding  coloring  matter;  it  is  very  soluble  in 
alcohol ;  insoluble  in  ether  and  hydrocarbons : 
these  solutions  possess  a  color  somewhat  similar 
to  that  of  the  field  violet.  Concentrated  sulphuric 
acid  dissolves  it,  forming  a  green  solution,  but 
excess  of  water  restores  it  to  its  original  color. 


ROSE  IN  E. 


87 


Like  aniline  purple,  reducing  agents  deprive  it 
of  its  color,  which  is  restored  by"  the  action  of  the 
atmosphere.  Tannin  produces  an  insoluble  com- 
pound with  it.  When  agitated  with  a  small 
quantity  of  binoxide  of  lead,  it  is  converted  into 
aniline  purple,  excess  of  this  reagent  changes  it 
into  roseine. 

§  3.  Roseine. 

This  substance  nearly  always  accompanies  ani- 
line purple,  though,  in  very  small  quantities.  It 
was  first  noticed  publicly  by  0.  Greville  Williams, 
and  afterwards  by  Dr.  David  Price.  Williams 
used  manganates  ifor  its  preparation,  but  Dr.  David 
*  Price  prepared  it  by  means  of  binoxide  of  lead. 
His  process  is  as  follows :  #To  a  boiling  solution  of 
one  equivalent  of  sulphate  of  aniline,  two  equiva- 
lents of  binoxide  of  lead  are  added,  and  the 
mixture  boiled  for  a  short  time.  The  rose-colored 
solution  is  then  filtered,  and  the  filtrate  evaporated 
to  small  bulk,  which  causes  a  certain  amount  of 
resinous  matter  to  be  separated;  this  evaporated 
solution  is  then  filtered,  and  the  coloring  matter 
precipitated  by  means  of  an  alkali,  it  is  then  col- 
lected on  a  filter,  slightly  washed,  and  then  dried. 
The  coloring  matter  thus  prepared,  readily  dis- 
solves in  alcohol,  forming  a  fine  crimson  colored 
liquid,  which  when  evaporated  to  dryness,  leaves 
the  coloring  matter  as  a  dark  brittle  substance, 
having  a  slightly  metallic  reflection.    It  is  much 


88  EMERALDINE,  OR  ANILINE  GREEN. 

more  soluble  in  water  than  either  aniline  purple 
or  violine,  but  like  them  it  is  insoluble  in  hydro- 
carbons, and  is  more  soluble  in  acids  than  in 
neutral  liquids.  Concentrated  sulphuric  acid  dis- 
solves it,  forming  a  green  solution;  excess  of 
water  restores  it  to  its  original  color.  It  forms  a 
compound  with  tannin  ;  and  is  also  decolorized,  or 
nearly  so,  by  powerful  reducing  agents. 

The  three  coloring  matters  just  mentioned, 
namely,  aniline  purple,  violine  and  roseine,  are 
evidently  closely  allied,  for  they  have  nearly  the 
same  properties.  They  are  all  formed  under  simi- 
lar circumstances,  namely,  by  the  action  of  oxidiz- 
ing agents  in  the  presence  of  water ;  they  are  all 
slightly  soluble  in  water,  though  as  the  shade  of  • 
color  becomes  redder,  so  their  solubility  increases; 
alkalies  precipitate  them  from  their  aqueous  solu- 
tions ;  concentrated  sulphuric  acid  dissolves  then^ 
forming  green  solutions  which  an  excess  of  water 
restores  to  the  original  color  of  the  coloring  mat- 
ters ;  powerful  reducing  agents  deprive  them  of 
their  color  or  nearly  so,  but  it  is  again  restored  by 
the  influence  of  oxygen ;  and  lastly,  tannin  forms 
insoluble  compounds  with  them  all. 

§  4.  Emeraldine  or  Aniline  Green. 

Most  chemists,  who  have  worked  with  aniline 
in  the  laboratory,  must  have  noticed  the  peculiar 
green-colored  substance  which  forms  on  the  out- 
side of  the  various  kinds  of  chemical  apparatus 


BLEU  DE  PARIS. 


89 


that  have  been  standing  in  the  vicinity  of  any 
quantity  of  this  body.  This  product  is  aniline 
green.  It  has  been  known  for  several  years;  it 
may  be  formed  by  various  processes.  One  consists 
in  oxidizing  aniline  with  chloric  acid;  this  is 
effected  by  mixing  an  hydrochloric  solution  of 
aniline  with  chlorate  of  potash.  It  r^iay  also  be 
obtained  by  oxidizing  a  salt  of  aniline  by  perchlo- 
ride  of  iron.  Obtained  by  either  of  these  processes, 
it  presents  itself  as  a  dull  green  precipitate,  which 
when  dried  assumes  an  olive  green  color.  It  is 
insoluble  in  water,  alcohol,  ether  and  benzole. 
Sulphuric  acid  dissolves  it,  forming  a  dirty  purple- 
colored  solution,  from  which  it  is  precipitated 
unchanged  by  water.  With  alkaline  solutions, 
it  changes  to  a  deep  color  somewhat  similar  to 
indigo,  but  acids  restore  it  to  its  original  color. 
The  color  of  aniline  green  is  much  enlivened  by 
the  presence  of  an  excess  of  acid,  but  unfortunately 
as  soon  as  this  acid  is  removed,  it  passes  back  to 
its  normal  color. 

§  5.  Bleu  de  Paris. 

This  is  another  coloring  matter  produced  under 
circumstances  similar  to  those  which  give  Fut- 
schine.  MM.  Persoz,  De  Luynes,  and  Salvetat 
give  the  following  account  of  its  preparation  and 
properties:  "9  grains  of  bichloride  of  tin  and 
16  grains  of  aniline  heated  for  thirty  hours  at  a 

8* 


90 


BLEU  DE  PARIS. 


temperature  of  about  356°  F.,  in  a  sealed  tube 
produce  neither  a  red  nor  a  violet,  but  a  very  pure 
and  lively  blue.*  Mr.  Perkins  repeated  the  ex- 
periment twice,  but  he  obtained  only  a  dirty  green 
color ;  but  at  last  he  obtained  the  blue  as  described 
by  MM.  Persoz,  De  Luynes,  and  Salvetat.  This 
blue  crystallizes  from  the  alcoholic  solution  in  the 
form  of  fine  needles,  having  the  aspect  of  ammo- 
niacal  sulphate  of  copper;  soluble  in  water,  alco- 
hol, wood-spirit  and  acetic  acid  ;  insoluble  in  ether 
and  bisulphide  of  carbon.  With  concentrated 
sulphuric  acid  it  forms  an  amber-colored  solution, 
which  water  converts  into  a  magnificent  blue  li- 
quid. Strong  nitric  acid  decomposes  it,  chromic 
acid  precipitates  it  from  its  aqueous  solution  with- 
out decomposition,  chlorine  destroys  it,  sulphurous 

*  When  you  break  the  tubes  in  which  the  reaction  has 
been  effected,  you  obtain  a  blackish  matter  which,  exhausted 
by  boiling  water,  colors  it  blue ;  the  solution,  treated  by 
common  salt,  left  to  precipitate  the  coloring  matter  that 
you  collect  on  a  filter,  whilst  the  liquor  takes  a  green  shade 
more  or  less  dark.  The  blue  precipitate  is  redissolved  anew 
in  water,  and  precipitated  again  by  the  chloride  of  sodium. 
This  operation  is  repeated  several  times  to  separate  com- 
pletely the  green  coloring  matter,  at  last  precipitate  by  few 
drops  of  hydrochloric  acid,  collect  the  blue  matter  on  a  filter, 
wash  first  with  water  acidulated  with  hydrochloric  acid, 
then  with  pure  water,  the  washing  is  terminated  when  the 
water  begins  to  pass  blue. 

To  obtain  it  crystallized,  dissolve  it  in  boiling  alcohol, 
which,  by  cooling,  deposits  it  in  form  of  fine  needles. 


I 


BLEU  DE  PARIS.  91 

acid  does  not  decolorize  it,  sulphide  of  ammonium 
is  without  action  upon  it.  It  is  precipitated  from 
its  aqueous  solution  by  alkalies  and  saline  com- 
pounds. Submitted  to  the  action  of  heat,  it  melts 
and  decomposes  in  giving  violet  vapors. 


I 


92  FUTSCHINE,  OK  MAGENTA. 


CHAPTER  XT. 

FUTSCHINE,  OR  MAGENTA. 

This  beautiful  product,  which  is  often  impro- 
perly called  Koseine,  is  a  member  of  an  entirely 
different  series  of  compounds  from  the  foregoing, 
being  formed  under  very  different  circumstances, 
and  possessing  very  different  properties.  This 
coloring  matter  was  first  observed  by  Natanson, 
in  1856,  when  studying  the  action  of  chloride  of 
Ethylene  on  aniline,  and  afterwards,  shortly  before 
it  was  practically  introduced  into  the  arts;  by  Dr. 
Hoffmann,  when  preparing  cyantrephenile-diamine 
by  the  action  of  bichloride  of  carbon  on  aniline. 
It  was  M.  Verguin  who  first  brought  it  forward 
as  a  dyeing  agent,  and  who,  we  believe,  taught 
manufacturers  how  to  prepare  it  on  a  large  scale. 
Futschine  is  invariably  formed  at  a  temperature 
ranging  from  17°  to  19°  Centigrade.  It  is  pro- 
duced from  aniline  by  the  action  of  reducible 
chloronized,  brominized,  iodized  or  fluorized  sub- 
stances, as  well  as  by  weak  oxidizing  agents. 
The  substances  used  for  its  preparation  on  the 
large  scale  are  perchlorides  of  tin  and  of  mercury, 


FUTSCHINE,  OR  MAGENTA. 


93 


and  the  nitrate  of  mercury.  It  has  also  been  pre- 
pared with  bichloride  of  carbon. 

Preparation  of  Futschine  by  the  action  of  Bichlo- 
ride of  Tin  on  Aniline, — Aniline  combines  with  bi- 
chloride of  tin,  evidently  producing  a  double  com- 
pound. This  product  is  a  white  substance,  and 
may  be  prepared  by  adding  to  aniline,  bichloride 
of  tin  in  the  anhydrous  state  or  dissolved  in  water. 
Anhydrous  bichloride  of  tin  combines  with  aniline 
with  great  energy  to  form  this  compound.  To 
prepare  Futschine  from  the  double  compound,  it  is 
necessary  that  it  should  be  free  from  water,  or 
nearly  so;  therefore  anhydrous  bichloride  of  tin  is 
generally  employed  for  its  preparation.  The  pro- 
cess adopted  is  as  follows :  anhydrous  bichloride 
of  tin  is  slowly  added  to  an  excess  of  aniline,  the 
mixture  being  constantly  stirred,  and  the  pasty 
mass  thus  formed  gradually  heated ;  as  the  tem- 
perature increases,  it  becomes  quite  liquid  and 
also  brown  in  color.  As  soon  as  the  temperature 
nearly  approaches  the  boiling  point,  the  mixture 
rapidly  changes  to  a  black-looking  liquid,  which, 
when  viewed  in  thin  layers,  presents  a  rich  crim- 
son color;  this  is  kept  at  its  boiling  point  some 
time,  and  then  well  boiled  with  a  large  quantity 
of  water ;  by  this  means  the  principal  part  of  the 
coloring  matter  is  extracted,  together  with  con- 
siderable quantities  of  tin  in  the  form  of  a  proto- 
compound.  The  aqueous  solution  of  the  coloring 
matter  and  hydrochlorate  of  aniline  is  then  boiled. 


94 


FUTSCHINE,  OR  MAGENTA. 


so  as  to  volatilize  any  free  aniline  it  may  contain, 
and  then  saturated  with  chloride  of  sodium.  The 
chloride  of.  sodium  causes  the  coloring  matter  to 
separate  as  a  semi-solid,  pitchy  substance  of  a 
golden  green  aspect,  while  the  hydrochlorate  of 
aniline  remains  in  solution.  The  coloring  matter 
thus  obtained,  may  be  further  purified  by  di- 
gestion wittr  benzole,  which  dissolves  out  a  cer- 
tain amount  of  resinous  matter. 

Preparation  of  Futschine  by  the  Action  of  Nitrate 
of  Mercury  on  Aniline. — When  protonitrate  of 
mercury  is  left  in  contact  with  aniline  for  some 
time,  it  forms  a  white  pasty  mass,  but  when  care- 
fully heated  to  170°  or  180°  Centigrade,  it  reacts 
upon  it,  forming  a  brown  liquid,  which  gradually 
changes  till  of  a  dark  crimson  color.  At  the 
same  time  the  whole  of  the  metal  of  the  mercury 
salt  collects  at  the  bottom  of  the  vessel  the  expe- 
riment is  conducted  in.  This  product,  when 
separated  from  the  metallic  mercury  and  allowed 
to  cool,  becomes  semi-solid,  being  filled  with 
crystals  of  nitrate  of  aniline.  To  purify  this  pro- 
duct it  is  best  to  dissolve  out  the  nitrate  of  aniline 
it  contains,  in  a  small  quantity  of  cold  water,  and 
then  to  boil  the  remaining  product  several  times 
with  fresh  quantities  of  water,  until  the  principal 
of  the  coloring  matter  is  extracted,  and  filter  the 
resulting  aqueous  solution  while  hot.  On  cool- 
ing, the  solution  will  deposit  the  coloring  matter 
as  a  golden-green,  tarry  substance,  from  which 


FUTSCHINE,  OR  MAGENTA. 


95 


benzole  separates  a  small  quantity  of  a  brown 
impurity,  leaving  the  coloring  matter  as  a  brittle 
solid. 

We  have  briefly  described  the  above  processes, 
because  they  may,  to  some  extent,  be  regarded  as 
types  of  most  of  the  methods  employed  for  the 
production  of  this  coloring  matter;  the  first,  re- 
presenting its  formation,  by  the  action  of  reduc- 
ible chlorides  upon  aniline,  and  the  latter  by  the 
influence  of  weak  oxidizing  agents. 

FutschinS  is  undoubtedly  an  organic  basis,  and 
a  more  powerful  one  than  is  generally  supposed. 
The  products  obtained  from  aniline  by  means  of 
bichloride  of  tin,  is  hydrochlorate  of  Futschine, 
and  that  obtained  by  the  oxidizing  action  of  ni- 
trate of  mercury,  is  the  nitrate  of  Futschine.  Our 
reason  for  stating  this  is,  that  on  examining  the 
coloring  matter  obtained  by  chloride  of  tin,  it  is 
found  to  contain  large  quantities  of  combined  hy- 
drochloric acid,  and  when  nitrate  of  mercury  was 
used,  considerable  quantities  of  combined  nitric 
acid,  therefore  we  conclude  that  the  former  is  the 
hydrochlorate  and  the  latter  the  nitrate. 

Futschine  is  separated  from  its  salts  by  precipi- 
tation with  a  small  quantity  of  ammonia.  When 
freshly  precipitated,  Futschine  is  a  red,  bulky 
paste,  which,  when  dry,  contracts,  forming  a 
purplish  red  powder.  It  is  difficultly  soluble  in 
water,  but  an  excess  either  of  hydrochloric  or  sul- 
phuric acid  dissolves  it,  forming  a  brownish  yellow 


96 


FUTSCHINE,  OK  MAGENTA. 


liquid,  from  which  ammonia  separates  it  un- 
changed. By  this  reaction  it  may  be  distinguished 
from  Eoseine,  which  dissolves  in  strong  sulphuric 
acid  producing  a  green  liquid.  Caustic  alkalies 
or  ammonia  i  n  excess  partially  precipitate  Futschine 
from  its  salts,  but  at  the  same  time  dissolve  a  con- 
siderable quantity  of  it,  forming  nearly  colorless 
liquids.  Acetic  acid  added  to  these  alkaline  solu- 
tions, restores  the  color  of  the  Futschine ;  and  if 
the  liquids  are  concentrated,  the  bases  precipitate 
it  as  a  red,  flocculent  substance.  An  alcoholic 
solution  of  Futschine,  when  evaporated  to  dryness, 
leaves  the  coloring  matter  as  a  brittle  mass,  having 
a  beautiful  golden-green  metallic  reflection.  By 
transmitted  light  it  has  a  red  color.  Futschine 
has  been  analyzed,  and  is  represented  by  the  for- 
mula, C12H12N20. 

In  the  hydrochlorate,  Mr.  Bechamp  found  a 
quantity  of  hydrochloric  acid  corresponding  with 
the  formula  C12H12N20  HC1.  He  also  examined 
the  hydrochloro-platinate  which  is  a  purple  pre- 
cipitate; it  has  the  formula  C12H12N°OHPtC]3. 
The  existence  of  oxygen  in  this  basis  is  remark- 
able, because,  in  many  instances,  it  is  produced 
from  agents  which  do  not  contain  a  trace  of  oxy- 
gen, as,  for  example,  bichloride  of  tin  and  aniline. 
The  only  way  to  account  for  the  presence  of  oxy- 
gen in  the  product  analyzed,  is  as  an  hydrate, 
thus : — 


FUTSCHINE,  OR  MAGENTA.  97 

Ci2Hi2N20  =  c,2H10N2  +  H20 

Futschine.  Anhydrous  Water. 

Futschine. 

This  is,  perhaps,  to  some  extent  confirmed  by 
an  experiment  made  with  iodaniline.  Iodaniline, 
when  heated,  yields  Futschine;  this  change  can  be 
expressed  thus : — 

2  (C6  [H6 1]  N)  =  C12H10N2  +*  2HI 

Iodaniline.  Anhydrous  Iodhydric 

Futschine.  Acid. 

But  supposing  the  Futschine  examined  by  Mr. 
Bechamp  to  have  been  an  hydrate,  it  is  remark- 
able that  its  hydrochlorate,  and,  more  particularly 
its  hydrochloro-platinate  should  also  be  hydrates ; 
but  as  our  knowledge  of  this  body  is  as  yet  but 
scanty,  we  must  wait  for  the  accumulation  of 
facts  before  we  can  form  any  fixed  opinion  respect- 
ing its  constitution.  The  compounds  investigated 
by  Mr.  Bechamp  appear  to  be  uncrystaliizable. 
Keducing  agents  decolorize  Futschine,  but  the 
oxygen  of  the  air  renders  it  its  color.  Like 
aniline  purple,  Futschine  is  a  very  intense  color- 
ing matter;  tannin  precipitates  both  Futschine 
and  its  salts,  forming  difficultly  soluble  substances. 
Bichloride  of  mercury  precipitates  this  substance 
and  its  salts,  forming  double  compounds;  when 
preparing  Futschine  by  means  of  bichloride  of 
tin,  there  are  two  coloring  matters  produced,  one 
possessing  an  orange  color,  and  the  other  a  purple 
hue.  Little  is  known  of  them. 
9 


98 


COLORING  MATTERS 


CHAPTER  XII. 

COLORING  MATTERS  OBTAINED  BY  OTHER  BASES 
FROM  COAL  TAR — NITROSO-PHENYLINE — DI-NI- 
TRO-ANILINE — NITRO-PHENYLINE — PICRIC  ACID 
— ROSOLIC  ACID — QUINOLINE. 

The  bases  toluidine,  xylidine,  and  cumidine, 
yield  coloring  matters  under  the  oxidizing  agents, 
and  also  when  submitted  to  the  action  of  reduci- 
ble chlorides,  at  high  temperatures,  analogous  to 
those  obtained  from  aniline  under  similar  circum- 
stances, but  the  results  generally  are  not  so  good, 
the  color  of  the  products  becoming  tinged  with 
brown,  as  the  bases  get  higher  in  the  series. 

Nitroso-Pheny  line. 

This  remarkable  body  is  obtained  by  the  action 
of  nascent  hydrogen  on  an  alcoholic  solution  of 
di-nitro-benzole.  It  is  represented  by  the  formula 
C6H6N20.  This  body  is  almost  insoluble  in  water, 
but  soluble  in  acids  and  in  alcohol,  producing 
crimson-colored  solutions,  but  its  color  is  not 
nearly  so  brilliant  as  that  of  Futschine.  Any 
experiments  with  it,  as  regards  its  dyeing  proper- 
ties, have  not  been  tried. 


OBTAINED  FROM  COAX  TAR. 


99 


Di-nitro- Aniline, 

Di-nitro-aniline  is  obtained  by  decomposing 
di-nitro-phenyle  citra-conamide  by  means  of  car- 
bonate of  soda.  When  pure,  it  crystallizes  in 
yellow  tables.  It  dissolves  very  sparingly  in 
water,  producing  a  yellow  liquid.  It  has  the 
formula  C6H5(N02)N2:  It  does  not  combine 
with  acids  or  alkalies,  although  it  appears  to  be 
more  soluble  in  acidulated  than  in  pure  waterc 
Silk  can  be  dyed  yellow  with  di-nitro-aniline. 

Nitro-phenylene  diamine,  or  Nitro-azo-phenylamine. 

Di-nitro-aniline,  when  submitted  to  the  action 
of  sulphide  of  ammonium,  changes  into  this  beau- 
tiful  base,  which  crystallizes  in  needles  of  a  red 
color,  somewhat  similar  in  appearance  to  chromic 
acid.  It  dissolves  in  water,  forming  a  yellow  or 
orange-colored  solution  like  that  of  bichromate 
of  potash.  Alcohol  and  ether  dissolve  it  freely. 
This  base  possesses  the  power  of  dyeing  silk  a 
very  clear  golden  color. 

Picric,  or  Dinitro-phenic  Acid. 

This  beautiful  acid  was  discovered  as  early  as 
1788,  by  Hausmann.  It  may  be  obtained  by  the 
action  of  heated  nitric  acid  on  a  great  variety  of 
substances.  The  following  are  the  names  of  some 
of  them :  Indigo,  Aniline,  Carbolic  acid,  Saligenine, 
Salicylious  and  Salicylic  acids,  Salicin,  Phlorizin, 


100 


COLORING  MATTERS 


Cumanin,  Silk,  Aloes,  and  various  Gum-resins.  It 
is  now  prepared  for  commercial  purposes  from 
carbolic  acid,  and  also  from  certain  gum-resins. 
We  have  prepared  it  from  carbolic  acid  on  a  large 
scale,  in  the  following  manner,  with  success:  As 
strong  nitric  acid  acts  very  violently,  when  brought 
in  contact  with  carbolic  acid,  we  have  found  it 
best  to  use  an  acid  having  a  gravity  less  than  1.3, 
so  as  partially  to  convert  the  carbolic  acid,  and 
afterwards  to  boil  it  in  stronger  acid  to  change  it 
into  picric  acid.  On  diluting  the  acid  solution,  the 
impure  picric  acid  precipitates;  to  further  purify 
this,  it  should  be  crystallized  from  boiling  water. 
When  preparing  this  product  for  commercial  pur- 
poses, it  is  advantageous  to  let  all  the  nitrous  fumes 
formed  in  its  preparation,  together  with  a  certain 
amount  of  atmospheric  air,  to  pass  over  a  fresh 
quantity  of  carbolic  acid.  This  will  absorb  them 
and  at  the  same  time  be  converted  into  nitro,  or 
di-nitro-phenic  acid,  and  consequently  diminish  the 
quantity  of  nitric  acid  required  for  its  manufac- 
ture. 

When  preparing  picric  acid  from  carbolic  acidj 
there  is  always  a  quantity  of  a  yellow,  resinous  mat- 
ter produced,  and  at  times  a  considerable  quantity 
of  oxalic  acid.  The  latter  is  always  produced  when 
the  acid  which  is  used  to  finally  convert  the  car- 
bolic acid  is  too  weak,  for  then  it  rapidly  decom- 
poses the  picric  acid,  yielding  carbonic  and  oxalic 
acids.   Picric  acid,  when  pure  and  dry,  is  of  a  light 


OBTAINED  FROM  COAL  TAR.  101 


primrose-yellow  color,  crystallizing  in  strongly- 
shining  lamina.  It  possesses  an  extremely  bitter 
taste,  and  dissolves  in  water  with  a  beautiful  yellow 
color.  When  digested  with  protoxide  of  iron,  in  the 
cold,  it  yields  a  brown  amorphous  compound,  which 
dissolves  in  water  with  a  blood  red  color.  Picric 
acid  was  introduced  as  a  dye  about  five  or  six 
years  since,  by  MM.  Guinon,  Marnas,  and  Bonney, 
eminent  silk  dyers  of  Lyons.  Many  of  the  cheap 
products  sold  as  picric  acid  are  of  a  brown  color, 
and  consist  of  impure  di-  and  tri-nitro-phenic  acids? 
and  sometimes  of  this  crude  product  and  ground 
turmeric. 

Rosolicacid. — Eunge  first  noticed  this  substance 
in  1834,  when  studying  creosote,  but  it  was  almost 
lost  sight  of,  until  again  observed  by  Dr.  Hugo 
Miller  only  a  short  time  since.  He  accidentally 
observed  that  when  crude  phenate  of  lime  is  ex- 
posed to  a  moist,  heated  atmosphere,  as  that  of  an 
ordinary  drying  stove,  it  gradually  changes  in 
color,  and  assumes  a  dark  red  tint ;  this  coloration 
is  owing  to  the  formation  of  rosolate  of  lime.  Dr. 
Muller  prepared  rosolic  acid  from  this  product  in 
the  following  manner  :  The  crude  rosolate  of  lime 
is  first  boiled  with  a  solution  of  carbonate  of  am- 
monia. By  this  means  a  crimson  solution  containing 
the  rosolic  acid  is  obtained ;  this  solution  is  then 
evaporated  nearly  to  dryness,  during  such  process 
ammonia  is  given  off,  and  the  crimson-colored 
liquid  gradually  changes  to  a  yellowish  red,  and 

9* 


102 


COLORING  MATTER 


at  the  same  time  a  dark  resinous  matter  separates ; 
the  resinous  substance  is  crude  rosolic  acid.  In 
order  to  purify  it,  it  is  submitted  to  the  following 
treatment,  proposed  by  Eunge :  The  crude  rosolic 
acid  is  dissolved  in  alcohol,  and  by  hydrate  of 
lime  in  slight  excess.  The  beautiful  crimson 
solution  which  is  thus  formed  is  agitated  for  some 
time  with  the  undissolved  portion  of  the  lime, 
filtered,  and  the  filtrate  diluted  with  water,  and, 
lastly,  the  alcohol  distilled  off.  The  residuary 
rosolate  of  lime  is  then  decomposed  with  just  a 
sufficient  quantity  of  acetic  acid,  and  the  whole 
boiled  until  every  trace  of  free  acetic  acid  and  still 
adhering  alcohol  is  volatilized.  The  rosolic  acid 
separates  first  as  a  red  precipitate,  but  when  heated, 
cakes  together,  forming  a  dark,  brittle  substance? 
having  a  greenish  metallic  lustre. 

It  may  be  still  further  purified  by  solution  in 
alcohol,  to  which  a  little  hydrochloric  acid  has 
been  added,  and  precipitation  with  water.  Pure 
rosolic  acid  is  a  dark  amorphous  substance,  pos- 
sessing the  greenish  metallic  lustre  of  cantharides. 
Its  powder  is  of  a  red,  or  rather  scarlet  shade, 
which,  if  rubbed  with  a  hard,  smooth  body,  assumes 
a  bright  gold-like  lustre.  In  thin  layers,  rosolic 
acid  presents  an  orange  color,  when  viewed  with 
transmitted  light,  but  with  reflected  light,  a  golden 
metallic  appearance.  When  thrown  down  from  an 
alcoholic  solution  with  water,  it  forms  a  flocculent 
precipitate  of  a  bright  red  color,  resembling  the 


OBTAINED  FROM  COAL  TAR.  103 


basic  chromate  of  lead.  Concentrated  acids,  as 
acetic,  hydrochloric,  and  sulphuric,  dissolve  rosolic 
acid,  forming  a  brownish  yellow  solution,  of  which 
water  precipitates  rosolic  acid  unchanged.  To  cold 
water,  it  imparts  a  bright  yellow  color,  and  is 
more  soluble  in  hot  than  cold  water.  Alcohol 
and  ether  dissolve  it.  With  ammonia,  caustic 
alkalies  and  caustic  earths,  it  forms  dark  red  com- 
pounds. These  compounds  are  very  unstable.  No 
precipitates  are  formed  with  aqueous  solutions  of 
the  rosolates,  with  the  basic  acetate  of  lead,  or  with 
any  other  metallic  salt.  According  to  Dr.  Muller, 
it  is  represented  by  the  formula  C23H2204.  Ko- 
solic  acid  has  been  prepared  lately  on  a  large  scale 
for  the  purpose  of  printing  muslin.  It  was  rosolate 
of  magnesia  which  was  employed.  It  is  not  used 
since  the  discovery  of  Futschine. 


104 


NAPHTHALINE  COLORS. 


CHAPTER  XIII. 

NAPHTHALINE  COLORS  —  CHLOROXYNAPHTHALIC 
AND  PERCHLOROXYNAPHTHALIC  ACIDS — CARMI- 
NAPHTHA  —  NINAPHTHALAMINE  —  NITROSO- 
NAPHTH  ALINE  —  NAPHTHAMEIN  —  TAR  RED  — 
AZULINE. 

The  beautiful  hydro-carbon  naphthaline,  which 
has  yielded  such  a  long  category  of  substances  to 
the  chemist,  up  to  the  present  time  has  yielded 
nothing  of  practical  importance  to  the  dyer.  From 
it,  the  following  color  derivatives  having  been  ob- 
tained, namely :  Chloroxy naphthalic  acid,  Perchlor- 
oxynaphthalic  acid,  Carminaphtha,  Ninaphthala- 
mine,  Nitrosonaphthaline  and  Naphthamein. 

Chloroxynaphtkalic  and  Perchbroxynaphthalic 
Acids. 

These  acids  were  discovered  by  Laurent.  They 
are  produced  by  digesting  the  chlorides,  namely : 
the  chloride  of  chloroxynaphthyle  and  the  chlo- 
ride of  perchloroxynaphthyle  with  an  alcoholic 
solution  of  hydrate  of  potash.  They  are  difficult 
to  obtain  in  quantity.  Mr.  Perkins  has  not  ob- 
tained satisfactory  results  in  their  preparation. 
They  have  the  formula  C10  (H5  CI)  O3  and  Cl0(H  CP) 


NAPHTHALINE  COLORS. 


105 


O3  respectively.  They  are  regarded  with  great 
interest,  as  being  very  closely  allied  with  alizarine, 
the  coloring  matter  of  madder;  in  fact  they  are 
viewed  as  chlor-alizaric  acid.  The  synopsis  is  based 
upon  the  idea  of  alizarine  having  the  formula  C10 
H6  O3,  but  it  happens  very  unfortunately  for  this 
theory,  that  the  formula  of  alizarine  itself  is  still  a 
disputed  point.  Chloroxynaphthalic  acid  is  of  a 
yellow  color,  insoluble  in  water  and  with  difficul- 
ty soluble  in  alcohol  and  ether ;  it  dissolves  in 
concentrated  sulphuric  acid.  This  acid  is  a  very 
sensible  test  for  alkalies,  being  changed  to  an 
orange  red  by  them.  This  may  be  shown  by 
moistening  paper  with  a  weak  alcoholic  solution 
of  this  acid,  drying  it,  and  then  exposing  it  to 
ammoniacal  vapors.  This  will  cause  it  to  assume 
a  red  color. 

The  chloroxyn aphtha! ates  are  described  as  pos- 
sessing great  beauty,  and  are  of  yellow,  orange, 
or  crimson  colors.  The  potash  salt  is  of  a  red 
crimson  color,  and  slightly  soluble  in  water ;  the 
baryta  salt  crystallizes  in  silky  needles,  having  a 
golden  reflection.  The  strontia,  lime,  alumina, 
and  lead  salts  are  of  an  orange  color ;  the  cadmium 
salt  is  a  vermilion  colored  precipitate ;  the  copper 
and  cobalt  salts  are  crimson  ;  and  the  mercury  salt 
is  of  a  red  brown  color.  Once  some  silk  was 
dyed  with  a  small  quantity  of  chloroxynaphthalate 
of  ammonia,  which  Mr.  Perkins  prepared,  and 
found  it  to  produce  a  good  golden  yellow  color, 


106 


NAPHTHALINE  COLORS. 


of  great  stabilty  under  the  influence  of  light. 
Perchloroxynaphthalic  acid  is  a  yellow,  crystalline 
body,  insoluble  in  water,  but  soluble  in  alcohol 
and  ether.  With  potash  or  ammonia  it  forms 
insoluble  salts  of  red  or  crimson  color  of  great 
beauty. 

Carminaplitha. 

This  coloring  matter  was  also  discovered  by 
Laurent.  It  is  obtained  by  heating  naphthaline 
with  a  solution  of  bichromate  of  potash,  and  then 
adding  sulphuric  or  hydrochloric  acids.  It  is 
described  as  a  fine  red  substance,  soluble  in  alka- 
lies, but  precipitated  from  its  alkaline  solutions 
by  means  of  acids.  Mr.  Perkins  never  obtained 
this  product  when  oxidizing  naphthaline. 

Ninaphthalamine. 
Ninaphthalamine  is  a  name  which  has  been 
given  to  a  remarkable  base  which  was  noticed  by 
Laurent  and  Zinin  ;  but  nothing  was  known  of  its 
nature  until  resubjected  to  investigation  by  Mr. 
Wood,  who  has  both  described  and  analyzed  it 
and  some  salts.  Its  formula  is  C10  (H8  NO)  N,  or 
naphthalamine  in  which  H  is  replaced  by  NO. 
Mr.  Wood  prepares  this  base  in  the  following 
manner:  Sulphuretted  hydrogen  is  to  be  passed 
through  a  boiling  solution  of  dinitronaphthaline 
in  weak  alcoholic  ammonia,  until  nearly  all  the 
alcohol  has  distilled  off,  which  operation  should 
occupy  two  or  three  hours.    The  residue  is  then 


NAPHTHALINE  COLORS. 

to  be  boiled  with  dilute  sulphuric  acid,  and  filtered. 
The  filtrate,  on  cooling,  deposits  an  impure  sul- 
phate of  ninaphthalamine  in  the  form  of  brownish 
crystals  which  are  purified  by  recrystallization  in 
water  two  or  three  times.  Mr.  Perkins  has  found 
when  crystallizing  this  salt,  that  it  is  best  to  use 
water  acidulated  with  sulphuric  acid.  When  pure, 
this  sulphate  has  to  be  decomposed  with  ammonia, 
and  the  resulting  precipitate  of  ninaphthalamine 
washed  with  water.  Thus  obtained,  ninaphthala- 
mine appears  as  a  bright  red-colored  crystalline 
precipitate,  which,  when  viewed  under  a  lens 
appears  as  beautiful  needles.  It  is  very  soluble 
in  alcohol,  producing  a  solution  which,  when  diluted, 
is  of  an  orange  color  slightly  tinged  with  brown, 
not  nearly  so  pure  in  color  as  that  of  nitropheny- 
linediamine.  It  is  slightly  soluble  in  water,  and 
possesses  the  power  of  dyeing  silk  with  a  color 
somewhat  similar  to  that  of  ordinary  annoto. 
With  acids  it  produces  colorless  salts.  Its  formula 
is  the  same  as  that  of  nitroso-naphthaline,  though 
it  possesses  v^ry  different  properties.  As  a  dyeing 
agent  we  do  not  think  it  would  be  of  any  value 
even  if  it  could  be  obtained  cheaply. 

Nitroso-naphtha  line. 

This  peculiar  body  is  a  product  of  the  action 
of  nitrous  acid  on  naphthalamine.  It  is  prepared 
by  mixing  a  solution  of  hydrochlorate  of  naphtha- 
lamine with  nitrate  of  potash.    From  this  mixture 


108 


NAPHTHALINE  COLORS. 


it  separates  a  reddish  brown  precipitate.  This, 
when  washed  with  water  on  a  filter  and  then  dried, 
is  dissolved  in  alcohol,  filtered,  and  evaporated  to 
dryness  on  the  water-bath.  Thus  prepared,  it  is 
a  crystalline,  dark-colored  substance,  having  a 
greenish  metallic  reflection.  It  is  soluble  in  al- 
cohol, and  also  in  benzole,  forming  orange  red 
solutions.  When  acids  are  added  to  an  alcoholic 
solution  of  nitroso-naphthaline  it  immediately 
assumes  a  most  beautiful  violet  color,  as  fine  as 
aniline  purple.  Alkalies  restore  it  to  its  original 
color.  Silk  may  be  dyed  a  beautiful  purple  shade 
with  this  substance,  provided  a  certain  quantity 
of  hydrochloric  or  sulphuric  acids  be  present.  But 
what  is  most  unfortunate  is,  that  when  the  silk, 
thus  dyed  is  rinsed  in  water,  the  color  immediately 
passes  back  to  that  of  the  pure  nitroso-naphthaline, 
and  also  that  the  amount  of  acid  required  to  keep 
up  the  purple  shade  if  left  in  the  silk  rots  it  in  a 
few  days.  Could  this  purple  be  fixed,  nitroso- 
naphthaline  would  be  a  cheap  and  most  useful 
dye.  Mr.  Perkins  has  endeavored  40  produce"  the 
sulpho-acid  of  nitroso-naphthaline,  thinking  that 
if  such  a  compound  could  be  obtained,  it  would 
possess  a  purple  color,  because  it  would  be  an  acid 
itself.  But  although  sulphuric  acid  does  dissolve 
it,  forming  a  blue  solution,  yet  no  combination 
takes  place.  He  also  endeavored  to  produce  this 
desired  result  by  treating  sulpho-naphthalamic  acid 
with  nitrous  acid,  but  obtained  only  nitroso-naph- 


NAPHTHALINE  COLORS. 


109 


thaline,  the  acid  of  the  sulpho-naphthalmic  acid 
having  apparently  separated. 

Naphthamein. 

Piria  observed  that  naphthalamine  and  its  salts 
produced  blue  precipitates,  afterwards  becoming 
purple,  when  brought  in  contact  with  perchloride 
of  iron,  terchloride  of  gold,  nitrate  of  silver,  and 
other  oxidizing  agents.  This  product  of  oxidation 
he  terms  naphthamein.  It  is  prepared  by  adding 
a  solution  of  perchloride  of  iron  to  a  solution  of 
hydrochlorate  of  naphthamein.  This  mixture  gra- 
dually changes  and  becomes  blue,  and  after  the 
lapse  of  a  short  time  deposits  a  blue  precipitate. 
This,  when  separated  by  means  of  a  filter,  is  washed 
with  water,  which  causes  it  to  change  in  color, 
until  a  reddish  brown  purple.  The  filtrate  from 
this  substance  contains  proto-chloride  of  iron,  and, 
according  to  Piria,  chloride  of  ammonium.  Naph- 
thamein, when  heated,  fuses  and  decomposes,  leav- 
ing a  residue  of  charcoal  behind.  It  is  insoluble 
in  water,  sparingly  soluble  in  alcohol,  but  more 
soluble  in  ether.  It  forms  a  blue  solution  with 
concentrated  sulphuric  acid,  and  is  precipitated 
from  this  solution  by  means  of  water.  Silk  and 
cotton  may  be  dyed  with  it,  but  the  color  of  this 
compound  is  so  inferior,  as  to  render  it  useless  as 
a  dyeing  agent. 


10 


110 


NAPHTHALINE  COLORS. 


Tar  Bed. 

This  coloring  matter  was  discovered  by  Mr. 
Clift,  of  Manchester,  in  1853.  It  is  obtained  by 
exposing  a  mixture  of  the  more  volatile  parts  of 
the  basic  oils  of  coal-tar  and  hypochlorite  of  lime 
to  the  air  for  about  three  weeks.  Of  the  pure 
coloring  matter  we  know  nothing,  except  that  with 
tannin  it  forms  an  insoluble,  or  difficultly  soluble 
substance.  With  different  mordants  it  yields  dif- 
ferent colors.  It  seems  probable  that  this  coloring 
matter  is  derived  from  pyrhole. 

Azuline. 

This  substance,  which  is  a  beautiful  blue  dye, 
has  been  introduced  within  the  last  year.  It  was 
discovered  by  MM.  Guinon,  Marnas  and  Bonney, 
of  Lyons,  who  keep  the  process  for  its  preparation  a 
secret.  It  is  obtained  from  coal-tar,  but  from 
which  of  its  numerous  derivatives  is  not  known. 
This  coloring  matter  is  a  brittle,  uncrystallizable 
body,  possessing  a  coppery,  metallic  reflection. 
It  is  very  difficultly  soluble  in  water,  but  soluble 
in  alcohol,  producing  a  magnificent  blue  solution, 
having  but  a  slight  tinge  of  red.  With  concen- 
trated sulphuric  acid  it  forms  a  blood-red  liquid 
which,  when  poured  into  an  excess  of  water,  pre- 
cipitates the  coloring  matter  unchanged.  Dilute 
acids  have  no  effect  upon  azuline.  Its  alcoholic 
solution,  when  mixed  with  an  alcoholic  solution 
of  hydrate  of  potash,  also  changes  to  a  dull  red 


NAPHTHALINE  COLORS. 


Ill 


color.  This,  when  diluted  with  water,  forms  a 
purple  liquid  which  is  gradually  restored  to  its 
original  blue  color  by  hydrochloric  acid.  With 
excess  of  ammonia,  the  solutions  of  azuline  change 
to  a  reddish  purple  color.  This  ammoniacal  solu- 
tion, when  treated  with  sulphide  of  ammonium, 
gradually  assumes  a  dull,  yellowish  brown  color. 
Iodine  destroys  the  color  of  azuline.  In  color  it 
is  not  quite  so  fine  as  chinoline  blue,  though  far  su- 
perior to  Prussian  blue. 


112        APPLICATION  OF  COAL  TAR  COLORS 


CHAPTER  XIV. 

APPLICATION  OF  COAL-TAR  COLORS  TO  THE  ART  OF 
DYEING  AND  CALICO  PRINTING. 

We  cannot  enter  fully  into  this  subject,  because 
we  do  not  feel  sufficiently  acquainted  with  the 
various  operations  of  the  dye  house  or  print  works 
to  do  so,  and  also  because  the  technical  details 
of  dyeing  and  printing  operations  would  not,  we 
think,  interest  the  reader.  We,  therefore,  propose 
to  speak  of  the  different  processes  employed  for 
dyeing  and  printing  with  coal-tar  colors,  in  gene- 
ral terms  only. 

Dyeing  Silk  and  Wool. 

Silk  and  wool  can  be  dyed  with  all  the  coal  tar 
colors,  with  the  exception  of  the  rosolates,  these 
fibres  possessing  in  most  cases  a  remarkable  affi- 
nity, if  we  may  so  speak,  for  these  coloring  matters. 
Many  of  them,  as  aniline  purple,  and  violine,  are 
taken  from  their  aqueous  solutions  so  perfectly  by 
these  substances  that  the  water  in  which  they  have 
been  dissolved  is  l^ft  colorless ;  in  fact,  silk  and 
wool  take  them  up  so  rapidly  that  one  of  the  great 
difficulties  the  dyer  has  to  contend  with,  is  to  get 
the  fibres  dyed  evenly. 


TO  THE  ART  OF  DYEING,  ETC. 


113 


To  Dye  Silk  with  Aniline  Purple,  Violine  and 
Roseine. 

One  process  is  applicable  for  dyeing  silk  with 
either  of  these  coloring  matters,  and  it  is  a  very 
simple  one.  An  alcoholic  solution  of  the  coloring 
matter  required,  is  to  be  mixed  with  about  eight 
times  its  bulk  of  hot  water  previously  acidulated 
with  tartaric  acid,  and  then  poured  into  the  dye- 
bath,  which  consists  of  cold  water  slightly  acidu- 
lated. After  being  well  mixed,  the  silk  is  to  be 
worked  in  it,  until  of  the  required  shade.  If  a 
bluer  shade  than  that  of  the  coloring  matter  is 
required,  a  little  solution  of  sulpho-indigotic  acid 
may  be  added  to  the  dye  bath,  or  the  silk  may  pre- 
viously be  dyed  blue  with  Prussian  blue,  or  any 
other  blue,  and  then  worked  in  the  dye-bath. 

To  Dye  Silk  with  Futschine,  Picric  Acid,  Ghinoline 
Blue  and  Violet, 

This  process  is  still  more  simple  than  the  above, 
as  it  is  simply  necessary  to  work  the  silk  in  cold, 
aqueous  solutions  of  these  coloring  matters.  With 
futschine  or  picric  acid,  a  little  acetic  acid  may  be 
used,  but  with  chinoline  colors,  acids  must  be  avoid- 
ed. With  picric  acid,  a  very  clear  green  color  maybe 
obtained  by  adding  a  little  sulpho-indigotic  acid 
to  the  dye-bath.  We  may  mention  that  violine  is 
not  of  such  a  fine  color  as  that  produced  by  aniline 
purple  and  indigo  blue ;  and  also  that  roseine  is 
not  such  a  good  color  as  futschine,  or  magenta. 

10* 


114        APPLICATION  OF  COAL  TAR  COLORS 


To  Dye  Silh  with  Azuline. 

The  dyeing  of  silk  with  this  coloring  matter  is 
far  more  difficult  than  with  the  preceding,  requir- 
ing to  go  through  two  or  three  different  processes. 
The  difficulty,  we  believe,  arises  from  the  insolu- 
bility of  azuline  in  water.  The  process  generally 
employed  is  to  work  the  silk  in  a  solution  of  the 
coloring  matter  acidulated  with  sulphuric  acid,  and 
when  of  a  sufficient  depth,  to  raise  the  temperature 
of  the  dye  bath  to  the  boiling  point,  and  work  the 
silk  in  it  again.  After  this,  the  silk  is  well  rinsed 
in  water  until  free  from  acid,  and  worked  in  a 
bath  of  soap  lather ;  it  is  then  again  rinsed  and 
finished  in  a  dilute  acid  bath. 

To  Dye  Wool  with  Aniline  Purple,  Violine,  JRoseine, 
Futschine,  etc. 

This  operation  is  generally  conducted  at  a  tem- 
perature of  5°  or  6°  Centigrade,  and  the  dye-bath 
is  composed  of  nothing  but  a  dilute  aqueous  solu- 
tion of  the  coloring  matter  required.  Acids  should 
be  avoided,  or  only  a  very  small  .quantity  used,  as 
the  resulting  colors  are  not  so  fine  when  they  are 
employed. 

Method  of  Dyeing  Cotton  with  Colors  of  Coal  Tar. 

When  aniline  purple  was  first  introduced,  con- 
siderable difficulty  was  experienced  in  dyeing  cot- 
ton so  as  to  obtain  a  color  that  would  resist  the 
action  of  soap.    Aniline  purple  is  absorbed  by 


TO  THE  ART  OF  DYEING,  ETC. 


115 


vegetable  fibres  to  a  certain  extent,  and  very  beau- 
tiful colors  may  be  obtained  by  simply  working 
cotton  in  its  aqueous  solution  ;  but  when  thus  dyed 
the  colors  will  not  stand  the  action  of  soap.  We 
have  tried  the  use  of  tin  and  other  mordants,  but 
without  any  satisfactory  result. 

In  1857,  Mr.  Puller,  of  Perth,  and  Perkins,  sim- 
ultaneously discovered  a  process  by  which  this  col- 
oring matter  could  be  fixed  upon  vegetable  fibres, 
so  as  to  resist  the  action  of  soap.  This  process  is 
based  upon  the  formation  of  an  insoluble  compound 
of  the  coloring  matter  with  tannin  and  metallic 
base  in  the  fibre.  To  effect  this  the  cotton  has  to 
be  soaked  in  a  decoction  of  sumach,  galls,  or  any 
other  substance  rich  in  tannin,  for  an  hour  or  two, 
and  then  passed  into  a  weak  solution  of  stannate 
of  soda,  and  worked  in  it  for  about  an  hour.  It 
is  then  wrung  out,  turned  in  a  dilute  acid  liquor, 
and  then  rinsed  in  water.  Cotton  thus  prepared  is 
of  a  pale  yellow  color,  and  has  a  remakable  power 
of  combining  with  aniline  purple. 

The  above  process  may  be  modified,  for  example: 
the  stannate  of  soda  may  be  applied  to  the  cotton 
before  the  tannin,  and  alum  may  be  used  in  the 
place  of  stannate  of  soda.  To  dye  this  prepared 
cotton  with  aniline  purple  it  is  only  necessary  to 
work  it  in  an  acidulated  solution  of  the  coloring 
matter ;  and  when  thus  prepared  the  cotton  will 
absorb  all  the  coloring  matter  of  the  dye-bath,  leav- 
ing the  water  perfectly  colorless.  It  has  been  found 


116        APPLICATION  OF  COAL  TAR  COLORS 


that  cotton  thus  prepared  can  be  dyed  with  any 
coloring  matter  that  forms  insoluble  compounds 
with  tannin,  therefore  it  is  used  for  dyeing  with 
roseine,  violine,  futschine,  and  chinoline  colors. 

Cotton  may  also  be  dyed  a  very  good  and  fast 
color  by  mordanting  it  with  a  basic  lead  salt  and 
then  working  it  in  hot  solution  of  soap  to  which 
aniline  purple  has  been  added.  Oiled  cotton,  such 
as  is  used  for  dyeing  with  madder,  is  also  used  in 
dyeing  these  colors.  Cotton  simply  oiled,  and 
before  mordanted  with  alum  and  galls,  also  com- 
bines rapidly  with  these  coloring  matters ;  but  as 
the  color  of  the  prepared  cotton  is  generally  rather 
yellow,  it  interferes  sometimes  with  the  beauty  of 
the  result.  Cotton  is  sometimes  coated  with  albu- 
men, which  is  coagulated  by  the  action  of  steam, 
and  the  albumen  which  covers  the  cotton  dyed  in 
the  usual  manner.  "We  may  mention  that  violine, 
roseine,  futschine,  and  also  the  chinoline  colors 
combine  with  unmordanted  vegetable  fibres,  as 
well  as  aniline  purple.  Picric  and  rosolic  acids 
are  not  applicable  for  dyeing  cotton. 

Printing  Calico  with  Coal  Tar  Colors. 

The  process  generally  employed  for  printing 
with  these  coloring  matters  is  simply  to  mix  the 
coloring  matters  with  albumen  or  lacterine,  print 
the  mixture  on  the  fibre,  and  then  to  coagulate 
the  albumen  or  lacterine  by  the  agency  of  steam. 
Mr.  Perkins  and  Mr.  Gray,  of  the  Dalmonach 


TO  THE  ART  OF  DYEING,  ETC.  117 


Print  Works,  discovered  the  first  process  of  ap- 
plying these  substances  to  fabrics  in  a  different 
manner  from  the  above.  It  consisted  in  forming 
a  basic  carbonate  or  an  oxide  of  lead  on  those 
parts  of  the  cloth  which  were  to  be  colored,  and 
then  working  the  cloth  thus  prepared  in  a  hot 
lather  containing  the  coloring  matter.  Where  the 
cloth  was  mordanted  with  the  lead  compound 
coloring  matter  was  absorbed ;  but  when  unmor- 
danted  it  was  left  white,  because  pure  cotton  is  not 
dyed  with  these  coloring  matters  in  the  presence 
of  soap.  This  procss  was  intended  for  the  appli- 
cation of  aniline  purple,  for  at  the  period  of  this 
discovery,  the  other  coal  tar  colors  were  unknown. 
Colors,  dyed  by  this  process  were  very  pure,  but 
it  had  many  disadvantages,  which  have  caused  it 
to  be  disused.  Lately  the  process  previously  de- 
scribed for  dyeing  colors  upon  cotton  prepared 
with  tannin  has  been  applied  to  calico  printing. 
It  consists  in  printing  tannin  in  the  fabric  pre- 
viously prepared  with  stannate  of  soda,  and  then 
dyeing  it  in  a  hot  dilute  acid  solution  of  the  color- 
ing matter.  By  this  means  the  parts  of  the  fabric 
which  are  covered  with  tannin  are  dyed  a  deep 
color,  but  the  other  parts  are  only  slightly  co- 
lored. These  are  cleared  by  means  of  well  known 
processes.  These  methods  of  applying  these  co- 
loring matters  is  also  modified  by  printing  a  com- 
pound of  the  coloring  matter  required  and  tannin 


118       APPLICATION  OF  COAL  TAR  COLORS 

on  the  prepared  cloth,  instead  of  tannin  only,  and 
then  steaming  the  goods. 

Method  of  Applying  Aniline  Green  to  Fabrics. 

This  process  is  interesting  as  being  the  first 
example  of  the  production  of  coal-tal  colors  on 
the  fabric  itself. 

The  process  is  very  simple.  The  design  is  to 
be  printed  on  the  cloth  with  a  thickened  solution 
of  chlorate  of  potash,  dried,  passed  through  a  solu- 
tion of  an  aniline  salt,  again  dried;  and  allowed  to 
hang  in  a  damp  atmosphere.  In  the  course  of 
two  or  three  days,  the  color  will  be  fully  deve- 
loped. The  color  thus  produced  may  be  changed 
into  a  dark  blue  by  the  agency  of  soap  or  an  al- 
kaline liquid.  The  quantity  of  aniline  used  in 
this  process  is  very  small. 

Application  of  Nitroso-naphthaline. 

If  cloth  is  printed  with  a  thickened  solution  of 
a  salt  of  naphthalamine,  dried,  and  then  passed 
through  a  solution  of  nitrate  of  potash,  nitroso- 
naphthaline  will  rapidly  make  its  appearance  as  a 
reddish  orange  color,  but  unfortunately  the  color 
thus  obtained  will  not  resist  well  the  action  of  soap. 

Of  the  numerous  coloring  matters  of  which  we 
have  briefly  spoken,  there  are  only  few  that  are 
at  present  employed  by  the  dyer  and  printer, 
namely;  Aniline  purple,  Futschine,  Picric  acid  and 
Azuline,  but  we  think  it  probable  that  others  of 


TO  THE  AKT  OF  DYEING,  ETC.  119 

them  will  soon  be  introduced,  such  as  the  Bleu  de 
Paris ;  and  Nitro-phenylenediamine  might  be  used 
for  silk  dyeing,  as  its  color  is  good  and  it  stand 
the  action  of  light  well.  Unfortunately  the  chino- 
line  colors  though  very  beautiful  are  most  fugitive. 
There  has  been  an  endeavor  to  introduce  the  chi- 
noline  blue  of  late,  but  although  a  considerable 
quantity  of  silk  was  dyed  with  it  at  first,  it  is 
now  scarcely  used,  because  when  exposed  to  the 
sun  for  two  or  three  hours  the  dyed  silk  becomes 
bleached.  Aniline  purple  resists  the  light  best, 
futschine  and  alpha  aniline  purple  soon  fade,  espe- 
cially on  cotton.  Aniline  and  bleu  de  Paris  are 
not  easily  acted  upon  by  light  when  on  silk. 

When  the  coloring  matters  of  coal  tar  were 
first  discovered,  there  was  a  great  fear  that  the 
workmen  engaged  in  their  manufacture  would 
suffer  in  health.  All  we  can  say  is,  that  during 
the  few  years  Mr.  Perkins  had  to  do  with  this 
branch  of  manufacture,  there  has  not  been  a  single 
case  of  illness  among  the  workmen,  that  has  been 
produced  by  any  operation  carried  on  for  the  pro- 
duction of  aniline  purple. 


120 


ACTION  OF  LIGHT  ON 


CHAPTER  XV. 

ACTION  OF  LIGHT  ON   COLORING   MATTERS  FROM 
COAL  TAR. 

We  think  it  will  interest  the  reader  to  give  him 
an  extract  of  a  paper  published  by  our  celebrated 
master,  M.  Chevreul,  on  this  subject.  We  trans- 
late it  literally  from  the  Comptes  Rendus  of  the 
Acad^mie  des  Sciences,  Seance  of  the  16th  July, 
1860,  vol.  li. 

Two  coloring  matters  recently  produced  are  of 
frequent  use,  one  to  dye  violet,  and  the  other 
red  violet.  Both  are  obtained  from  aniline. 
This  basis,  under  the  influence  of  hypochlorites, 
gives  the  violet,  and  treated  by  the  anhydrous 
bichloride  of  tin  gives  the  red  violet,  or  futschine. 
Any  coloring  matter  cannot  be  compared  to  the 
Futschine  for  the  brightness,  intensity,  and  purity 
of  the  color.  It  dyes  the  silk  in  1st  red  violet, 
red  violet,  5ih  violet,  and  you  can  raise  a  gam  from 
the  white  till  the  11th  shade,  from  the  shade  4th 
till  the  8th;  we  have  the  color  called  rose.  Car- 
thamine  applied  on  silk  gives,  generally,  colors 
from  the  3d  red  violet  to  the  red,  it  can  be  then 
two,  three,  four  or  five  gams  of  my  chromatic 


COLORING  MATTERS  FROM  COAL  TAR.  121 

circle  comprised  between  the  color  of  the  Futschine 
and  that  of  the  carthamine,  both  applied  on  silk. 
Before  the  futschine,  carthamine  was  used  to  give 
the  finest  rose,  but  it  was  a  rose  less  violet,  whilst 
futschine  gives  a  rose  to  the  5th  violet  of  the  red 
violet,  or  the  1st  red  violet,  ordinary  color  of  the 
rose. 

The  roses  of  cochineal  are,  for  the  brightness 
and  intensity,  to  the  roses  of  carthamine  that  these 
are  to  the  roses  of  futschine.  Ladies  who  like  the 
rose  must  avoid  to  place  themselves  near  those 
who  wear  the  rose  of  futschine  or  cochineal,  if 
they  wear  themselves  the  rose  of  carthamine.  If 
thanks  are  due  to  the  author  of  the  discovery  of 
futschine,  it  is  not  a  reason  to  have  this  color  ap- 
plied on  silk  used  for  curtains,  tapestry,  etc.,  for 
if  futschine  has  the  beauty  of  the  rose  it  has  also  its 
fragility.  It  is  enough  of  four  hours  of  exposition 
to  the  sun,  to  have  the  silk  dyed  with  futschine 
to  become  tarnish,  turn  vinous,  and  afterwards 
reddish. 

Futschine  on  cotton  is  not  stable.  A  card  of 
specimens  of  wool,  silk,  cotton,  dyed  with  futs- 
chine and  carthamine,  shows  that  futschine  applied 
on  silks  is  inferior  in  stability  to  the  carthamine,  for 
the  silk  dyed  with  this  latter  has  an  orange  color 
more  sensible  that  the  one  dyed  with  futschine, 
which  has  a  violaceous  color,  and,  however,  that  one 
had  been  raised  to  the  8th  shade,  whilst  the  speci- 
men dyed  with  carthamine  had  been  only  to  the 
11 


122 


ACTION  OF  LIGHTS.  ON 


6,  5th  shade.  When  the  red  violet  of  futschine 
is  changed  after  four  hours  exposition  to  the  sun, 
the  red  violet  of  cochineal  has  not  changed  after 
one  week  to  the  same  exposition.  Silk  mordanted 
with  alum  and  cream  tartar  and  dyed  in  red 
violet,  9th  shade,  that  is  the  shade  above  crimson, 
after  an  insolation  of  eight  months  has  lost  only 
8  shades.  At  last  silk  dyed  in  1st  red  violet,  10th 
shade,  with  cream  tartar  and  tin  composition  lost 
in  the  same  length  of  time  l-5th  shade. 

I  have  demonstrated  in  1837  the  influence  of 
oxygen  atmospheric  in  about  every  case,  which,  in 
stuffs  dyed  with  organic  coloring  matters,  are  dis- 
colorized  by  their  exposition  to  the  sun,  in  proving 
that  the  same  can  be  kept  several  years  in  lumi- 
nous vacuo.  I  have  demonstrated,  in  the  same 
year,  that,  on  the  contrary,  Prussian  blue  is  de- 
colorized in  luminous  vacuo;  it  becomes  first  white, 
then  brownish,  and  is  recolorized  by  the  contact 
of  oxygen.  To-day  I  present  to  the  Academy 
results  very  different ;  they  have  been  given  by 
picric  acid  used  in  dyeing  since  about  20  years. 

Cold  it  gives  to  the  wool,  yellow,  8th  shade ;  to 
the  silk  2d  yellow  5th  shade.  Boiling  it  gives  to 
the  wool  the  3d  orange  yellow  9th  shade,  to  the 
silk  the  1st  yellow  6th  shade ;  in  both  cases  it 
does  not  fix  to  the  cotton.  It  is  very  curious  to 
follow  the  changes  that  the  wool  and  silk  expe- 
rience under  the  influence  of  luminous  air;  they 
are  described  in  the  following  table :— 


COLORING  MATTERS  FROM  COAL  TAR. 


123 


After  6  days' 


Color  of  the  Silk, 
insolation  yellow 


9th  shade. 


u 

18  " 

a 

5th  or.  yellow 

9th 

u 

1  month 

u 

4th  " 

9-5th 

u 

2  " 

ct 

3d  " 

9th 

u 

3  ■ 

a 

3d  " 

9-8th 

a 

4  " 

a 

1st  " 

7-5th 

u 

5  " 

tt 

1st  " 

7-5th 

u 

6  " 

ft 

"  l-10th 

6-25th 

a 

8  " 

tt 

5th       "  2-10th 

3d 

Color  of  the  Wool. 
After  6  days'  insolation  3d  orange  yellow  9-5 th  shade. 


18  " 

1  months' 

2  " 

3  " 

4  " 

5  " 

6  " 
8  " 


3d  « 

2d  " 

orange  yellow 
tt 

5th  orange 
4th  " 
3d  « 
3d  " 


9-5th 

10th 

10-5th 
a 

11th 

10-75th 
10-75th 
11th 


These  results  are  curious  when  you  compare 
them  to  the  proceedings.  This  progression  by 
which  the  wool  in  8  months  gained  2  shades  in 
passing  from  the  5th  orange  yellow  9th  shade,  to 
the  3d  orange  11th  shade,  that  is,  passing  by  8 
gams  towards  the  red.  The  silk,  after  gaining  4 
shades,  almost  near  the  red,  has  begun  to  descend 
from  the  3d  month. 

Reflections. 

This  is  an  important  question  to  know  if  in  the 
trade  the  buyer  is  not  exposed  to  pay  very  dear, 
a  color  beautiful  without  doubt,  but  having  no 
stability  whatever,  in  the  quality  of  the  tissue. 


124    ACTION  OF  LIGHT  ON  COLORING  MATTERS. 

This  inconvenience  is  a  real  one,  and  this  reflec- 
tions have  for  object  not  to  destroy  but  attenuate 
them. 

Industry  is  free  to  manufacture  any  kind  of 
colors,  except  in  the  case  of  a  special  convention 
between  the  manufacturer  and  the  buyer. 

The  merchant  cannot  be  responsible,  but  it  is 
to  the  buyer  to  have  the  merchant  indicate  on 
his  bill  the  name  of  the  matter  used  to  dye  the 
stuff,  by  example  if  it  is  a  crimson  or  a  rose  that 
the  buyer  wants  sold,  he  will  have  the  bill  with 
the  denomination  of  crimson  or  rose  of  cochineal. 
I  speak  here  only  for  stuffs  used  in  tapestry,  and 
I  do  not  refer  to  the  roses  of  futschine  and  car- 
thamine  employed  for  dresses. 

If  buyers  were  knowing  the  difference  which 
exists  between  stuffs  of  the  same  color,  but  dyed 
with  different  matters,  we  are  certain  that  before 
long,  our  stores  will  not  have  other  colors  than 
those  known  to  be  solids;  and  if  in  a  public 
place,  the  public  had  on  the  eyes  two  comparative 
tables,  one  dye  with  all  colors  which  have  been 
exposed  to  the  sun  a  certain  length  of  time,  and 
the  other  with  the  same  colors  kept  in  the  dark, 
the  public  will  be  soon  instructed  of  the  extreme 
difference  existing  between  colors,  and  this  in- 
struction will  be  the  best  warrant  to  not  be  de- 
ceived in  the  trade  of  colors.  We  hope  to  see 
some  enterprising  houses  establish  such  tables, 
and  we  are  sure  they  will  render  a  great  service 
to  the  public  at  large. 


LATEST  IMPROVEMENTS,  ETC. 


125 


CHAPTER  XVI. 

LATEST  IMPROVEMENTS  IN  THE  ART  OF  DYEING. 
CHRYSAMMIC  ACID  —  MOLYBDIC  AND  PICRIC 
ACIDS — EXTRACT  OF  MADDER. 

Chrysammic  Acid. 

Lately  a  color  prepared  with  aloes  has  been 
used  to  dye,  and  its  fine  properties  deserve  to  attract 
the  attention  of  dyers.  Messrs.  Sacc  and  Schlum- 
berger  have  given  a  great  attention  to  this  pro- 
duct. We  shall  give  its  preparation  and  its  uses 
to  dye  as  described  by  Schlumberger. 

Preparation  of  the  Coloring  Matter. 

In  a  retort  of  a  capacity  of  22  to  28  gallons, 
introduce  67  pounds  of  commercial  nitric  acid 
and  add  to  it  about  18  ounces  of  aloes  of  the  best 
quality.  Heat  the  retort  in  a  water  bath  under  a 
chimney,  when  nitrous  vapors  begin  to  disengage, 
take  out  the  fire  and  introduce  in  the  retort  by 
small  portions  10  lbs.  of  aloes.  When  all  the 
aloes  has  been  introduced  and  the  disengagement 
of  nitrous  vapors  has  stopped,  pour  the  whole  in  a 
flat  dish  and  evaporate  in  paste  in  a  sand  bath, 

and  terminate  the  evaporation  to  dryness  in  a 

11* 


126 


LATEST  IMPROVEMENTS  IN 


water  bath.  Put  the  mass  on  a  filter  and  wash  it 
several  times  with  cold  water  and  dry  at  a  gentle 
heat. 

The  product  in  dye  is  of  about  66|  per  cent,  of 
the  aloes  used.  The  cost  for  2  J  pounds  are  about 
$1.40. 

Dyeing  of  Wool  with  Chrysammic  Acid. 

If  you  dissolve  in  a  kettle  full  of  river  water, 
2  lbs.  12  ounces  of  aloes  purple,  that  you  boil 
and  refresh,  and  introduce  in  this  bath  34  pounds 
of  well  washed  wool,  this  wool,  after  an  hour  of 
ebullition,  takes  a  fine  brown  color.  If  the 
quantity  of  chrysammic  acid  is  double,  you  obtain 
a  fine  velvet  black. 

If  you  dissolve  1  pound  11  ounces  of  chry- 
sammic acid  in  water,  to  which  you  add  2^  lbs. 
of  calcined  soda,  you  obtain  a  liquid  of  a  very  fine 
purple  color,  which  after  a  few  days  is  very 
intense,  and  which  can  communicate  to  34  pounds 
of  wool,  by  an  ebullition  of  half  an  hour,  a  fine 
bluish  color.  The  wool  wants  to  be  well  washed; 
but  do  not  require  any  mordant.  If  for  the  same 
quantity  of  wool  you  use  the  double  of  purple 
of  aloes,  you  obtain  a  blue  similar  to  the  blue  of 
indigo  by  the  vat. 

If  you  neutralize  the  filtered  liquor  collected 
from  the  washings  of  chrysammic  acid  obtained 
by  evaporation,  with  a  paste  of  chalk,  and  you 
filter  the  neutralized  liquor,  you  can  obtain  with 


THE  ART  OF  DYEING. 


127 


this  liquor,  several  shades  more  or  less  light  of 
olive  green,  according  to  the  concentration  of  the 
bath. 

At  last  chrysammic  acid  receives  again  a  very 
important  application,  in  the  use  of  it  to  fix  other 
colors  which  are  not  solid. 

If  you  add  6f  lbs.  of  orseille  and  9  ounces  of 
purple  of  aloes  dissolved  in  caustic  soda,  you 
obtain  an  orseille  color  on  which  air  and  light 
have  no  action. 

The  extract  of  orseille  found  in  the  trade,  com- 
municates to  wool  brighter  colors  than  common 
orseille,  but  they  are  not  solid.  Mr.  Schlumberger 
has  found  that  in  mixing  11 J  lbs.  of  this  extract 
with  18  ounces  of  dry  aloes  purple,  and  leaving 
the  mixture  several  days,  the  colors  obtained  are 
solid  and  kept  all  their  beauty. 

Chrysammic  acid  then  is  one  of  the  most  solid 
colors  that  the  wool  dyer  can  find,  and  it  deserves 
a  more  attentive  study. 

Molybdic  and  Picric  Acid. 

1.  It  is  only  since  a  short  time  that  molybdic  acid 
is  used  in  the  art  of  dyeing  and  different  modes 
for  its  preparation  have  been  indicated. 

The  molybdic  acid  can  be  prepared  in  the 
following  manner.  Melt  together  equal  weights 
of  molybdate  of  lead  reduced  to  fine  powder,  with 
calcined  soda,  in  an  iron  crucible,  decant  the 
formed  molybdate  of  soda,  then  prepare  with  hot 


128 


LATEST  IMPKOVEMENTS  IN 


water  a  concentrated  solution  of  this  molybdate 
that  you  decompose  by  an  excess  of  nitric  acid, 
and  you  boil  till  the  molybdic  acid  separates  in 
the  form  of  a  fine  yellow  precipitate ;  this  precipi- 
tate is  washed  with  water  and  at  last  dried. 

The  molybdate  of  ammonia  is  prepared  in  the 
following  manner:  Introduce  little  by  little  in 
caustic  ammonia,  molybdic  acid,  as  much  as  it  can 
be  dissolved.  The  dissolution  of  molybdic  acid  is 
accompanied  by  a  disengagement  of  heat,  and 
presents  itself  in  the  form  of  a  light  yellow  color, 
which  has  a  very  strong  ammoniacal  smell,  and 
must  be  kept  out  of  the  contact  of  the  air. 

I  give  now  the  different  processes  to  dye  stuffs 
with  these  preparations. 

Dyeing  of  Silk. 

You  can  obtain  a  very  dark  blue  in  impreg- 
nating silk  with  molybdate  of  ammonia :  you  leave 
to  dry,  and  pass  in  a  bath  of  hydrochloric  acid, 
and  immediately,  without  washing,  in  a  bath  of 
chloride  of  tin,  to  develop  the  blue  color;  wash 
well  and  dry.  You  can  obtain  lighter  shades  in 
diluting  the  molybdate  of  ammonia  with  water. 
Silk  impregnated  with  a  solution  of  molybdate  of 
soda,  at  20°  B.,  dried  and  pass  in  hydrochloric  acid 
and  chloride  of  tin  baths,  takes  a  nice  blue  color. 
In  diluting  the  molybdate  of  soda  with  water,  you 
can  obtain  lighter  shades. 

These  colors  are  very  solid  to  the  light. 


THE  ART  OF  DYEING. 


129 


Dyeing  of  Cotton. 

The  color  on  cotton  appears  less  fine  than  on 
silk.  The  finest  and  darkest  blues  are  obtained 
with  the  molybdate  of  ammonia;  but,  if  the  bath 
is  diluted  with  three  times  its  volume  of  water, 
you  have  then  a  gray-blue. 

We  have  not  the  least  doubt  that  before  many 
years  this  substance  will  be  used  by  all  the  pro- 
fession. 

2.  Picric  acid  has  been  employed  first  by  Mr. 
Guinon  of  Lyons,  France,  in  the  dyeing  of  silk 
and  wool.  Its  process,  to  manufacture  it  by  treat- 
ing coal  tar  by  nitric  and  sulphuric  acids,  he  ob- 
tains a  resinoid  matter,  which,  dissolved  in  more 
or  less  water,  gives  the  shade  wanted.  It  is  in 
this  bath,  heated  at  105°,  that  he  passes  the  silk 
without  mordant,  and  he  introduces  it  afterwards 
in  the  warm  room,  without  washing,  to  fix  the 
color. 

The  process  to  prepare  it  consists  in  heating 
coal  tar,  and  to  introduce  into  it  three  times  its 
weight  of  nitric  acid ;  that  you  let  run  in  it  by  a 
small  glass  pipe:  boil  with  the  acid  till  in  a  syrupy 
consistence ;  wash  several  times  with  cold  water, 
and  afterwards  with  warm  water,  to  separate  the 
acid  from  the  resinoid  matters,  and  evaporate  it 
to  dryness  to  obtain  crystals. 

15|  grs.  of  picric  acid,  dissolved  in  a  sufficient 
quantity  of  water,  could  dye,  in  yellow, 
pounds  of  silk. 


130 


LATEST  IMPROVEMENTS  IN 


Silk  cloths  take  in  it  a  very  fine  shade,  with- 
out alterating  their  brightness.  The  results  are 
the  same  with  wool.  With  potash  the  shades  can 
vary  till  yellow  orange. 

For  more  details  on  this  acid,  we  refer  to  Chap- 
ter VII. 

Madder. 

Madder  is  one  of  the  coloring  matters  which 
has  been  the  most  studied  in  these  last  times. 
That  plant  has  been  submitted  to  many  treat- 
ments in  "order  to  extract  from  it  its  pure  coloring 
matter.  We  shall  enumerate  briefly  some  of  the 
most  important  treatments  which  have  been  tried 
on  this  plant. 

Extract  of  Madder  by  Messrs.  Julian  and  Roguer. 

They  operate  on  madder  in  powder;  they  shake 
it  conveniently  in  large  vats,  with  cold  or  hot 
water,  deprived  of  calcareous  salts.  They  run  it 
in  vat- filters. 

According  to  the  colors  they  wish  to  obtain, 
they  leave  the  madder  thus  in  paste  in  the  vat- 
filters  from  one  to  five  days,  according  to  the  want 
or  not  of  an  alcoholic  fermentation.  This  paste  is 
then  well  pressed  and  carried  into  ovens  to  be  dried. 
The  water  collected  after  the  pressure  is  submitted 
to  the  alcoholic  fermentation. 


THE  ART  OF  DYEING. 


131 


Extract  of  Madder  by  Koecklin. 

His  process  gives  an  extract  of  madder  free  of 
ligneous  matters,  and  the  colors  obtained  in  dye- 
ing are  as  good  and  solid  as  madder  itself.  He 
uses  the  neutral  organic  oxides,  such  as  acetone, 
hydrate  of  methylene,  alone  or  combined  with 
alcohols  or  heterogenous  substances.  These  oxides 
are  used  as  solvents  of  the  coloring  matter. 

It  is  by  maceration  and  expression  that  he  sa- 
turates the  solvent;  the  bath  being  saturated,  he 
precipitates  the  coloring  matters  by  water,  i. 
till  water  does  not  produce  any  precipitate.  The 
precipitate  filtered  and  dried  constitutes  the  ex- 
tract of  madder. 

It  is  a  known  fact,  that  in  the  use  of  madder  in 
dyeing,  they  utilize  only  two-thirds  of  the  color- 
ing matter,  the  last  is  retained  in  the  residuum. 
Mr.  Schwarts  tried  many  experiments,  the  object 
of  which  was  to  utilize  this  coloring  matter,  and 
he  has  not  succeeded.  The  best  process  he  found 
is  the  following: — 

He  takes  7  pounds  14  ounces  of  commercial 
sulphuric  acid,  and  reduces  it  at  60°  B. ;  after  it  is 
cooled,  he  adds  to  it  6 \  ounces  of  flour  of  madder, 
which  is  equivalent  to  13  ounces  of  washed  mad- 
der. He  leaves  to  macerate  half  an  hour  and  throws 
the  whole  on  a  flannel:  the  filtration  is  slow,  and  the 
filtrate  is  of  a  very  dark  orange  color.  He  pours 
this  liquid  in  half  a  gallon  of  water,  which  preci- 


132     LATEST  IMPROVEMENTS  IN  ART  OF  DYEING. 

pitates  all  the  coloring  matter,  and  then  filters  a 
second  time  through  a  thick  flannel  cloth.  The 
filtrate  is  an  acid  which  marks  35°  B. 

The  two  matters  left  on  the  filters  are  perfectly- 
washed  with  water,  dried  and  weighed,  they  give 
three  ounces  of  residuum,  with  a  tinctorial  power 
equal  to  six  ounces  of  madder,  and  half  an  ounce 
of  extract,  equal  to  fifteen  ounces  of  madder.  For 
the  acid  at  35°,  it  can  be  used  again  in  bringing 
it  at  60°  by  distillation. 


THEORY  OF  COLORING  MATTERS,  ETC.  133 


CHAPTBE  XVII. 

THEORY  OF  THE  FIXATION  OF  COLORING  MATTERS 
IN  DYEING  AND  PRINTING. 

There  are  two  methods  of  coloring  stuffs  which 
must  not  be  confounded  with  each  other.  By  one 
of  these,  the  coloring  matters,  lakes,  etc.,  are  mixed 
with  gums  or  varnishes  to  make  them  into  a  color 
which  is  applied  to  the  stuff,  and  which,  on  drying, 
adheres  to  it.  Whether  these  coloring  matters 
are  mixed  with  a  fat  varnish,  drying  oil,  white  of 
egg,  the  result  is  always  the  same ;  but  this  opera- 
tion, which  is  purely  mechanical,  and  which  may 
be  performed  on  every  kind  of  fabric,  will  only 
occupy  the  printer's  attention  so  far  as  relates  to 
the  discovering  of  that  glutinous  body  which  is 
most  capable  of  rendering  this  or  that  colored  sub- 
stance adherent  to  such  or  such  fabric.  By  the 
other  method  the  coloring  matters,  brought  to  the 
proper  conditions,  are  deposited  and  then  fixed 
on  the  goods  in  such  a  manner  as  to  be  incorpo- 
rated with  the  fibre,  and  only  to  be  capable  of  being 
detached  from  it  by  the  intervention  of  a  more  or 
less  powerful  chemical  agent;  but  some  of  them 
— and  in  this  number  are  several  substances  of  the 
12 


134     THEORY  OF  THE  FIXATION  OF  COLORING 


organic  kingdom,  such  as  indigotin,  carthamin, 
curcumin,  and  among  the  mineral  colors;  the  ox- 
ides of  iron,  chromium,  lead,  etc. —  only  require  to 
be  applied  on  the  goods ;  whilst  a  greater  number 
of  others,  such  as  madder,  cochineal,  Brazil  and 
Campeachy  woods,  quercitron,  and  weld,  unite 
with  the  different  fibres  only  by  the  co-application 
of  auxiliaries,  which  are  designated  by  the  name 
of  mordants  ;  it  is  in  consequence  of  this  difference 
that  all  who  have  written  on  dyeing  have  divided 
coloring  matters  into  those  which  adhere  to  the  goods 
of  themselves,  and  those  which  can  only  be  fixed  by 
the  co-application  of  mordants. 

To  discover  the  cause  in  virtue  of  which  the 
different  colored  bodies  unite  with  the  textile  fibres 
of  cotton,  wool,  and  silk,  to  such  a  degree  as  to 
form  with  them  one  body ;  to  explain  how  it  hap- 
pens that  one  and  the  same  substance  has  not  the 
same  aptitude  for  each  of  these  fibres — such  is  the 
question  which  first  presented  itself  to  the  scien- 
tific men  who  devoted  their  attention  to  the  appli- 
cation of  colors,  and  the  solution  of  which  is  more 
especially  important  to  the  art  of  dyeing,  of  which 
the  printing  of  fabrics  is  but  a  particular  case. 
Hellot  and  Le  Pileur  d'Apligny,  Macquer, 
Berthollet,  Bergmann,  and  Chevreul,  who 
are  justly  entitled  to  rank  as  high  authorities  on 
this  subject,  have  given  forth  different  opinions 
on  this  point.  The  first  two  saw  in  the  fixation 
of  the  colors  on  the  goods  only  a  purely  mechani- 


MATTERS  IN  DYEING  AND  PRINTING.  135 

cal  operation ;  the  last  four,  on  the  contrary,  only 
an  operation  purely  chemical. 

Of  all  chemists  Mr.  Chevreul  is  the  one  who  has 
searched  most  deeply  into  this  important  matter, 
and  in  comparing  the  general  phenomena  of  dye- 
ing with  those  which  natural  philosophers  and 
chemists  generally  consider  as  dependent'  on  mo- 
lecular forces,  the  causes  of  chemical  action,  he 
arrives  at  the  conclusion,  that  the  first  are  of  the 
number  of  those  which  take  place  when  two  or 
more  bodies  are  in  contact  and  their  combination 
is  effected  slowly. 

It  appears  therefore  that  whilst  Hellot  and 
d'Apligny  attribute  all  the  effects  produced  by 
coloring  matter,  to  the  existence  in  the  fibres,  of 
pores  more  or  less  numerous  and  spacious,  in 
which  the  coloring  matter  lodges,  all  chemists 
repudiate  this  view,  and  trace  the  same  effects  to 
chemical  affinity. 

Such  were  the  notions  entertained  by  scientific 
men  on  the  causes  of  the  adherence  of  coloring 
matters  to  the  goods,  when  the  views  of  Mr. 
Walter  Crum  were  published.  According  to 
the  experiments  of  de  Saussure,  experiments  so 
full  of  interest  and  so  well  known,  chemists  were 
aware  that  charcoal  absorbs  gases  without  altering 
their  nature,  in  proportions  which  vary  according 
to  the  nature  of  these  gases,  its  own  nature,  and  its 
state  of  porosity.  No  one  is  now  ignorant  of  the 
applications  which  are  daily  made  of  this  body  in 


136     THEORY  OF  THE  FIXATION  OF  COLORING  „ 

the  arts,  for  decoloring  syrups,  by  freeing  them 
from  different  substances.  It  is  in  connection 
with  this  order  of  facts,  and  enlightened,  more- 
over, by  the  theoretic  works  of  the  celebrated 
chemist  of  Berlin,  that  Mr.  Crum  proceeds  to  ad- 
duce arguments  in  favor  of  the  ideas  of  Hellot. 
He  advances,  in  fact,  after  passing  in  review  the 
different  modes  of  action  of  porous  bodies,  that 
several  dyeing  operations  depend  on  the  capillary 
action  described  by  de  Saussure ;  and  this  opinion 
he  bases  chiefly  on  the  result  of  the  microscopic 
examination  of  the  fibres  of  cotton,  which  was 
made  by  Mr.  Thompson,  of  Clitheroe,  and  M. 
Bauer — this  examination  having  established  that 
these  fibres  are  formed  of  transparent  and  glass- 
like tubes,  which,  though  cylindrical  before  their 
maturity,  flatten,  on  the  contrary,  from  end  to 
end,  as  they  ripen,  and  then  present  the  aspect  of 
two  separate  tubes.  Mr.  Crum  thinks  that,  since 
the  sides  of  these  tubes  permit  water  to  pass 
through,  they  must  be  porous;  but  he  adds,  that 
neither  the  form,  nor  even  the  existence  of  such 
lateral  perforations  have  been  capable  of  being 
discovered  by  the  aid  of  the  most  powerful  mi- 
croscope. This,  as  will  be  seen,  is  the  hypothesis 
put  forward  by  Le  Pileur  d'Apligny,  presented 
under  a  new  form,  and  with  the  reserve  of  a  mind 
essentially  experimental.  This  being  assumed, 
the  eminent  Scottish  manufacturer  explains  the 
fixation  of  the  colors  in  the  following  manner. 


MATTERS  IN  DYEING  AND  PRINTING.  137 

He  first  admits  that  the  mineral  base  of  a  madder- 
dyed  color — oxide  of  iron  or  aluminium — treated 
with  a  volatile  acid — acetic  acid,  for  example — 
gives  rise  to  a  solution  which,  when  impressed  on 
the  fabric,  is  there  gradually  decomposed  in  course 
of  time,  abandoning  its  acid,  just  as  it  would  be  de- 
composed in  similar  circumstances  without  the  inter - 
vention  of  the  cotton;  and  if  this  base,  deposited  on 
the  fabric,  remains  adhering  to  it  so  powerfully  as 
to  resist  the  action  of  the  most  perfect  washing,  it 
is  because  the  solution,  after  having  penetrated  by 
the  lateral  openings  into  the  interior  of  the  tubes 
which  compose  the  cotton,  is  there  decomposed, 
and  the  oxide  being  set  free  in  the  narrow  pas- 
sage where  it  is  enclosed,  can  no  longer  be  disen- 
gaged from  it.  When  the  cotton,  then,  composed 
of  sacs  thus  lined  with  metallic  oxide,  passes  into 
a  madder-bath,  or  one  of  any  other  coloring  mat- 
ter, the  latter  combines  with  the  metallic  oxide  by 
a  true  chemical  action  to  form  a  lake,  or  what  is 
properly  called  a  color. 

Such  are,  in  few  words,  the  principal  considera- 
tions which  this  chemist  brings  to  bear  on  the 
question.  Persoz  holds  a  different  opinion,  and 
proceeds  to  examine  how  far  this  theory,  which, 
by  the  author's  admission,  has  several  points  of 
resemblance  to  that  of  Hellot  ;  and  Le  Pileur 
d'Apligny,  admits  of  being  supported  by  the  facts 
on  which  it  is  based.  The  following  are  Persoz's 
views  on  the  subject: — 

12* 


188     THEORY  OF  THE  FIXATION  OF  COLORING 

According  to  the  first  proposition,  the  acetate 
of  alumina,  for  example,  would  be  decomposed  in 
presence  of  the  goods,  just  as  if  it  were  free,  and 
experience  seems  to  him  to  be  here  opposed  to 
such  an  assertion.  He  does  not  dispute  that  this 
salt,  free,  or  in  presence  of  the  goods,  is  composed 
of  acetic  acid  and  alumina,  or  basic  acetate;  but 
that,  for  equal  quantities,  and  diffused  over  equal 
surfaces  of  cotton  cloth,  plates  of  glass,  mica,  or 
platinum,  and  dried,  moreover,  in  the  same  condi- 
tions, this  acetate  gives  up  always  the  same  quan- 
tity of  alumina,  is  what  he  finds  it  impossible  to 
admit.  In  fact,  if  the  desiccation  takes  place  at  a 
temperature  but  little  elevated,  the  quantity  of  the 
earth,  taken  from  the  acetate  by  the  cotton,  will 
be  incomparably  greater  than  that  which  would 
be  liberated  on  the  glass  or  mica  plates;  it  must 
be  concluded,  therefore,  that  the  textile  fibre  of 
the  cotton  exercises  a  powerful  influence  on  the 
decomposition  of  the  acetate  of  alumina.  But  if 
any  doubt  still  exist  as  to  the  part  which  the  fibre 
performs  in  the  decomposition  of  a  mordant,  the 
subjoined  fact  ought,  he  thinks,  to  dispel  tbem. 
A  solution  of  cubical  alum,  submitted  to  sponta- 
neous evaporation,  yields  crystals  of  cubical  alum ; 
but  if  one  puts  in  it,  for  a  certain  time,  stuffs  of 
silk  and  cotton,  this  same  solution  now  furnishes, 
after  undergoing  a  spontaneous  evaporation,  no- 
thing but  octahedral  crystals  of  alum,  deprived  as 


it  is  by  these  stuffs  of  a  notable  portion  of  its 
base. 

The  organic  and  inorganic  kingdoms,  espe- 
cially the  former,  furnish  a  great  number  of  sub- 
stances which  possess  the  property  of  dyeing 
stuffs,  either  constituting  colors  by  themselves,  or 
entering  as  elements  into  compounds  of  a  more 
complicated  nature;  but,  to  receive  an  application, 
these  substances,  simple  or  complex,  must  unite, 
if  not  by  themselves,  at  least  by  the  intervention 
of  a  suitably  selected  body,  two  essential  qualities: 
first,  that  of  being  insoluble  or  nearly  so;  second, 
that  of  resisting  as  much  as  possible  the  destructive 
action  of  the  air  and  the  solar  rays.  The  first  of 
these  qualities  is  indispensable;  for  if  it  be  want- 
ing, there  is  coloration  of  the  goods,  but  not  dyeing, 
in  the  proper  sense  of  the  word;  a  simple  washing 
with  water  suffices  to  discharge  the  color.  The 
second  is  not  essential  in  the  same  degree,  since 
it  is  subordinate  to  the  stability  which  is  intended 
to  be  given  to  the  colors  applied  to  a  fabric. 

Indigotin,  carthamin,  curcumin,  oxide  of  iron, 
oxide  of  chromium,  sulphide  of  arsenic,  sulphide 
of  antimony,  are  dyeing  substances  by  themselves. 
When  one  interrogates  experiment  as  to  the 
means  of  making  them  adhere  to  the  goods,  so 
strongly  as  to  constitute  one  body  with  them,  it 
is  found  to  be  necessary  either  to  form  these  co- 
lors on  the  stuff  itself,  by  putting  in  presence  of 
the  latter  the  elements  of  which  they  consist,  and 


140     THEORY  OF  THE  FIXATION  OF  COLORING 


one  of  which  at  least  must  be  soluble,  or,  if  these 
tints  are  previously  formed,  to  make  them  enter 
into  a  soluble  combination  with  which  one  im- 
pregnates the  fabric  to  set  them  afterwards  at 
liberty,  in  such  a  condition  that  they  combine  with 
the  fabric  in  the  nascent  state,  either  as  protoxide, 
which,  by  oxidizing  in  the  air,  passes  by  degrees 
into  the  state  of  sesquioxide,  or  in  the  state  of 
sesquioxide  at  first.  The  color  of  sesquioxide  of 
chromium  is  fixed  only  in  the  same  conditions. 
Again,  to  make  the  sulphides  of  antimony  and 
arsenic  adhere,  it  is  sufficient  to  apply  to  the 
goods  one  of  the  saline  and  soluble  combinations 
of  these  bodies,  then  to  decompose  it  by  an  acid 
so  as  to  set  them  at  liberty.  The  fixation  of  car- 
thamine  takes  place  under  circumstances  nearly 
similar. 

The  greater  part  of  coloring  matters — nine- 
tenths  at  least — are  not  of  a  dyeing  power  by 
themselves,  and  only  become  so  by  entering  into 
a  combination  which  has  for  its  object,  not  only 
to  give  them  the  first  quality  essential  to  every 
tint  for  being  fixed,  insolubility,  but  oftener  also 
to  make  them  contract  a  shade  which  they  do 
not  assume  by  themselves.  The  coloring  matter 
of  madder,  for  example,  which  is  soluble  in  water, 
acquires  the  property  of  dyeing  only  in  so  far  as 
it  is  combined  with  a  body  capable,  in  the  first 
place,  of  forming  with  it  an  insoluble  compound, 
as  certain  fatty  substances,  the  oxides  of  aluminum, 


MATTERS  IN  DYEING  AND  PRINTING.  141 


tin,  iron,  et  cetera,  and  then  making  it  contract  the 
hue  which  one  desires  to  obtain. 

The  different  dye  woods  do  not  dye  better  by 
themselves  than  madder ;  and  they  require,  like 
it,  to  enter  previously  into  a  combination. 

Chromic  acid  itself,  rich  as  it  is  in  color,  becomes 
a  dyeing  substance  only  so  far  as  it  forms  part  of 
a  saline  combination,  which  should  present,  along 
with  the  shade  desired,  the  greatest  possible  insolu- 
bility. Even  the  alumina,  which  serves  as  a  base 
to  all  the  organic  colors,  is  not  capable  of  fixing 
the  chromic  acid. 

It  is  only  in  so  far  as  they  are  formed  on  the  stuffs 
themselves,  that  the  dyeing  compounds  of  this 
group  become  adherent  to  them.  In  any  other 
case  there  is  no  dyeing,  unless,  as  sometimes  hap- 
pens, the  combination  becomes  by  slow  degrees 
insoluble,  either  by  itself — carthamin — or  by  the 
intervention  of  a  suitable  agent — catechu.  Ex- 
perience proves,  moreover,  that  of  the  two  sub- 
stances which  usually  occur  or  co-operate  to  the 
formation  of  the  color,  it  is  that  which  is  insoluble 
which  should  be  fixed  first  on  the  fabric,  and  with 
the  same  precautions  as  if  one  were  dealing  with 
one  of  the  substances  which  are  of  a  dyeing  nature 
when  used  by  themselves.  The  dyer  deviates 
from  this  rule,  only  in  so  far  as  the  elements  of 
the  lake,  happening  to  be  equally  soluble,  and 
endued  moreover  with  an  equal  inclination  for  the 
fibre  of  the  stuff,  render  it  a  matter  of  indifference 


142  THEORY  OF  THE  COLORING 


whether  the  latter  be  first  impregnated  with  the 
one  or  the  other:  thus  the  colored  combination 
which  is  formed  by  nut-gall  and  a  ferruginous 
preparation,  is  rendered  adherent  either  by  first 
depositing  the  iron  compound  on  the  fabric,  and 
afterwards  passing  the  latter  into  a  decoction  of 
nut-gall,  or  by  commencing  with  impregnating 
the  stuff  with  this  infusion,  to  pass  it  afterwards 
into  a  ferruginous  preparation. 

This  rapid  glance  at  the  formation  and  fixation 
of  dyeing  substances,  will  doubtless  suffice  to 
make  it  understood  that  the  subject  under  con- 
sideration presents  different  orders  of  facts,  which 
it  is  necessary  not  to  confound.  In  the  fixation  * 
of  indigo,  for  example,  there  are,  on  the  one  hand, 
the  formation  of  indigo-blue,  and  on  the  other, 
the  adherence  of  the  latter  to  the  stuff.  The  first 
of  these  facts  enters  into  the  phenomena  of  oxi- 
dation that  are  best  defined ;  the  second  into  those 
of  adherence  or  juxtaposition,  which  are  con- 
founded more  or  less  with  the  facts  pertaining  to 
the  aggregation  of  similar  particles.  In  the  fixa- 
tion of  the  color  of  madder,  and  of  all  its  con- 
geners, there  are  in  like  manner  two  orders  of 
facts :  the  one  which  relates  to  the  most  clearly 
understood  chemical  actions — namely,  the  union 
of  this  coloring  matter  with  the  oxide,  which  is 
called  in  to  give  it,  besides  the  insolubility  neces- 
sary to  it,  the  desired  shade;  the  other,  which 
consists  in  the  juxtaposition  and  adherence  to  the 


MATTERS  IN  DYEING  ANL>  PRINTING.  143 


stuff,  of  the  lake  which  it  produces.  So,  in  the 
fixation  of  chromic  acid,  considered  as  a  coloring 
matter,  it  is  necessary  to  distinguish  between  the 
formation  of  the  colored  saline  compound  which 
one  wishes  to  obtain,  and  its  fixation,  properly 
speaking,  on  the  fabric.  There  are,  therefore,  in 
all  the  operations  of  dyeing  and  of  the  fixation  of 
the  colors,  certain  phenomena,  which,  inasmuch 
as  they  belong  to  the  most  common  chemical  re- 
actions, cannot  give  rise  to  any  discussion ;  let  it 
now  be  considered  whether  it  be  not  possible  to 
dissipate  likewise  all  uncertainty  in  what  concerns 
the  others. 


144  PRINCIPLES  OF  THE  ACTION  OF 


CHAPTER  XVIII. 

PRINCIPLES  OF  THE  ACTION  OF  THE  MOST  IMPORT- 
ANT MORDANTS. 

Hitherto,  the  term  mordant  has  been  applied 
to  every  substance  which  possesses  the  twofold 
property  of  uniting,  on  the  one  hand,  with  the 
goods,  and  on  the  other  with  the  coloring  matters. 
From  this,  it  might  appear  that  the  mordants 
possess  properties  quite  peculiar,  whilst  in  reality 
it  is  not  so.  Placing  one's  self  in  the  point  of  view 
which  accords  with  the  theory  advanced  by  Per- 
soz,  one  sees  in  these  bodies  only  the  elements, 
the  constituent  principles,  of  a  saline  compound 
which  forms  on  the  fabric  itself  to  become  adhe- 
rent to  it. 

From  the  fact  that  the  colorable  and  colored 
principles  all  combine  with  the  metallic  oxides  to 
form  insoluble  compounds,  it  would  seem  also 
that  these  last  should  all  be  capable  of  fulfilling 
the  part  of  mordants,  and,  consequently,  of  be- 
coming the  base  of  the  colored  lakes  formed  on 
the  stuff.  It  is  not  so,  however ;  the  number  of 
bodies  which  possess  this  property  is  very  limited. 
They  are,  among  the  compounds  of  the  inorganic 


THE  MOST  IMPORTANT  MORDANTS.  145 

kingdom,  the  oxides  of  aluminium,  iron,  chromium, 
and  tin ;  among  the  products  of  the  organic  king- 
dom, the  modified  fatty  bodies.  The  Editor  has 
already  pointed  out  a  resemblance  of  the  oxides 
of  aluminum,  iron,  and  chromium  among  them- 
selves, observing  that  the  volume  of  their  equiva- 
lents is  the  same;  considered  under  another  re- 
lation, these  three  compounds  are,  of  all  the 
metallic  oxides,  those  which  exhibit  in  the  highest 
degree  the  property  of  passing  from  a  state  in 
which  they  possess  their  full  aptitude-  for  com- 
bining, to  an  isomeric  state  in  which  they  become 
indifferent  in  the  presence  of  the  most  energetic 
agents. 

For  a  body  to  be  capable  of  performing  the 
part  of  a  mordant,  it  is  necessary,  in  accordance  . 
with  the  views  already  stated,  that  the  dimensions 
of  its  molecules  be  in  a  simple  ratio  to  those  of 
the  surface  of  the  fibre,  and  that,  being  fixed  on 
the  fabric,  it  give  rise  to  a  colored  compound,  the 
faces  of  which,  being  also  in  a  simple  relation  with 
those  of  the  fibre,  cause  its  adherence. 

All  the  mordants  do  not  in  the  same  manner 
render  the  colors  adherent  to  the  stuffs;  some 
cause  them  to  undergo  only  slight  changes  of 
shade,  depending  on  the  acid  or  basic  character 
which  the  mordant  performs,  and  especially  on 
the  dimensions  of  the  colored  molecule  which  is 
formed.  Thus,  let  hydrate  of  lead,  on  the  one 
hand,  be  deposited  on  a  stuff,  and  on  the  other, 
18 


146  PRINCIPLES  OF  THE  ACTION  OF 


hydrate  of  alumina,  both  colorless,  but  possessed 
of  different  properties,  and  let  this  stuff  be  passed 
into  a  bath  of  cochineal ;  the  aluminous  mordant 
will  be  dyed  red,  and  the  lead  mordant  a  deep 
black.  The  same  will  be  the  case,  and  for  the 
same  reason,  with  hydrate  of  tin  and  hydrate  of 
alumina,  which,  if  fixed  on  a  stuff  and  dyed  in  a 
madder  bath,  will  give — the  latter,  a  red  inclining 
to  rose- violet,  the  former,  a  red  inclining  to  orange. 
The  others,  particularly  the  oxide  of  iron,  cause 
the  colorable  or  colored  principle  to  previously 
undergo  an  alteration ;  for,  if  the  iron  oxide  com- 
bined purely  and  simply  with  the  coloring  matter 
of  the  madder,  for  example,  which  in  its  state  of 
isolation  is  of  a  clear  brown  or  orange-yellow,  one 
„  should  obtain  lakes  of  a  clearer  color  than  that 
which  is  peculiar  to  this  oxide,  whilst  lakes  are 
produced  of  which  the  shade  varies  from  the  most 
intense  black  to  the  most  delicate  lilac,  according 
to  the  proportion  of  oxide  on  the  stuff. 

The  nature  of  the  principal  mordants  being 
known,  the  first  point  to  be  investigated  is  this — 
whether  it  be  a  matter  of  indifference  to  employ 
one  saline  combination  rather  than  another,  to 
render  their  base  adherent  to  the  goods  ?  There 
are,  in  this  question,  two  points  to  be  considered : 
the  first  is  one  which  the  manufacturer  should 
never  lose  sight  of  in  the  operations  by  which  he 
applies  a  mordant  on  the  goods,  namely,  the  che- 
mical part  which  this  mordant,  once  fixed,  ought 


THE  MOST  IMPORTANT  MORDANTS.  147 

to  fulfil  in  presence  of  the  coloring  matter.  Sup- 
pose, for  example,  that  instead  of  having  set  at 
liberty  on  the  goods  hydrated  alumina  in  that  state 
in  which  it  has  all  its  chemical  properties,  it  has, 
in  point  of  fact,  been  deposited  thereon  in  that 
state  in  which  it  loses  momentarily  all  its  aptitude 
for  combining — the  operation  will  be  a  failure,  and 
goods  thus  mordanted  will  not  dye.  The  second 
point  is  this,  namely,  that  the  brightness  and  in- 
tensity of  the  color  which  is  obtained  from 
a  mordant  depend  on  the  manner  in  which  this 
mordant  is  set  at  liberty,  and  passes  into  the  inso- 
luble state  on  the  fibre,  to  be  brought  into  imme- 
diate contact  with  it.  Thus,  let  hydrate  of  alumina 
be  prepared  with  every  precaution,  let  one  part 
of  it  be  slowly  dried,  and  another  quickly,  and 
there  will  be  obtained,  in  the  first  case,  a  coherent 
mass  of  a  horny  aspect,  in  the  second,  a  dull  and 
opaque  mass ;  and  these  two  pieces,  immersed  in 
a  solution  of  coloring  matter  of  pure  madder,  will 
be  dyed,  the  one  of  a  red  almost  brown,  the  other, 
a  dull  and  pale  red.  It  is  important,  therefore,  to 
seek,  among  saline  combinations,  that  which  yields 
most  easily  to  the  goods  the  base  which  it  contains, 
and  which  is  required  to  perform  the  part  of  a 
mordant,  by  preserving  to  this  base  all  its  chemi- 
cal power,  and  the  physical  state  most  favorable 
to  the  reflection  of  the  luminous  rays. 


148 


ALUMINOUS  MORDANTS, 


CHAPTEE  XIX. 

ALUMINOUS  MORDANTS. 

The  aluminous  compounds  which  are  used  to 
deposit  on  stuffs  the  oxide  of  aluminum  in  the 
state  in  which  it  acts  as  a  mordant,  by  attracting 
to  it  and  fixing  the  coloring  matter  of  a  dye-bath, 
are  of  two  kinds.  In  some,  the  alumina  is  in  the 
state  of  a  base ;  in  others,  it  performs  the  part  of 
an  acid. 

In  the  basic  state,  there  are  as  many  aluminous 
salts  as  acids,  but  all  of  them  cannot  be  employed 
as  mordants,  those  which  are  insoluble  are  taken 
off,  by  the  slightest  washing,  from  the  stuff  on 
which  they  are  applied ;  such  are  the  tri-basic  sul- 
phate, the  phosphate,  the  phosphite,  the  arseniate, 
the  borate  of  alumina,  et  cetera.  Those  which  are 
soluble  behave  in  three  different  manners :  some 
are  basic,  or  capable  of  becoming  so  by  giving  up 
a  part  of  their  acid,  and  therefore  require  to  be 
only  deposited  on  a  fabric  to  yield  to  the  fibre, 
either  in  the  cold  or  with  the  aid  of  a  temperature 
more  or  less  elevated,  all  or  part  of  the  alumina 
which  they  contain :  such  are  the  pure  or  impure 
acetate  of  alumina,  cubic  alum,  oxalate  of  alumina 


ALUMINOUS  MORDANTS. 


149 


the  butyrate  and  the  formiate.  Others,  either 
neutral  or  containing  an  excess  of  acid,  are  divi- 
ded into  two  groups ;  1st,  the  salts  of  alumina  in 
which  the  oxide  is  not  masked,  and  which,  conse- 
quently, may  always  become  mordants  or  yield 
their  oxide  to  the  goods  when  their  acid  is  satu- 
rated with  no  base,  or  when,  by  the  aid  of  another 
salt,  by  double  decomposition,  the  formation  of  a 
new  aluminous  salt,  insoluble  and  adherent  to  the 
stuff,  is  determined ;  to  this  category  belong  the 
sulphate,  the  seleniate,  the  chlorate,  the  bromate, 
the  iodate,  the  bi-phosphate,  the  bi-arseniate,  the 
nitrate,  the  chromate,  the  chloride,  the  bromide, 
the  iodide,  and  octahedral  alum  ;  2d,  the  salts  of 
alumina  of  which  the  base  is  masked,  and  which, 
saturated  by  an  oxide,  or  mixed  with  another  salt, 
would  never  furnish  to  the  fabric  an  aluminous 
compound,  insoluble,  adherent,  and  capable  of 
attracting  the  coloring  matter.  It  is  in  this  group 
that  the  tartrate,  the  citrate,  and  the  malate  of 
alumina  range  themselves.  Thus,  with  the  excep- 
tion of  these  last  three,  it  may  be  said  that  all  the 
compounds  of  alumina  can  serve  for  mordants; 
with  this  difference,  nevertheless,  that  some  re- 
quire only  to  be  deposited  on  the  stuff,  at  a 
temperature  more  or  less  elevated,  to  fix  their 
base  upon  it,  while  others  would  remain  upon  it 
indefinitely  without  giving  up  alumina  to  the 
fabric,  if  by  the  intervention  of  something  the 
base  did  not  become  free  and  insoluble.  This 

13* 


150 


ALUMINOUS  MORDANTS. 


will  be  better  understood  by  repeating  the  follow- 
ing experiments  of  Persoz.  After  previously 
scouring  with  an  acid  from  all  foreign  matters, 
the  samples  of  calico,  A,  B,  C,  D,  E,  he  impreg- 
nated— 

Sample  A  with  a  solution  of  acetate  of  alumina  at  6°  Twad- 
dell; 

Sample  B  with  a  solution  of  nitrate  of  alumina  in  the  pre- 
ceding liquor,  and  marking  12°  Twaddell ; 

Sample  C  with  a  solution  of  nitrate  of  alumina  at  6°  Twad- 
dell; 

Sample  D  with  a  solution  of  alum  in  an  acetate  of  alumina  at 

3°,  and  marking  9°  Twaddell ; 
Sample  E  with  a  solution  of  alum  marking  9°  Twaddell ; 

and  these  samples,  dried  at  the  same  temperature, 
in  the  same  conditions,  then  rinsed  several  times 
in  distilled  water,  lastly  dyed  in  a  madder  bath, 
were  found  as  follows : — 

Sample  A,  charged  with  coloring  matter  of  an 
intensity  proportional  to  the  quantity  of  oxide 
yielded  to  the  fabric  by  the  acetate. 

Sample  B — though  impregnated  with  a  prepara- 
tion containing  much  more  alumina — was  dyed  a 
much  weaker  shade,  showing  the  influence  of  the 
nitrate  which  always  renders  the  decomposition 
of  the  acetate  a  little  more  difficult. 

Sample  C,  always  colorless  when  the  nitrate  of 
alumina  employed  contained  one  equivalent  of 
base  for  three  equivalents  of  acid,  and  the  cloth 
on  which  it  was  applied  was  entirely  freed  from 
the  calcareous  substances  with  which  it  is  some- 


ALUMINOUS  MORDANTS. 


151 


times  charged  on  coming  from  the  operations  of 
bleaching,  which  are  always  finished  with  washings 
in  water. 

Sample  D,  of  a  shade  less  intense,  by  half,  than 
that  of  sample  A,  so  that  the  alum  associated  with 
the  acetate  of  alumina  was  a  pure  loss  in  the  pro- 
cess. 

Sample  E,  colorless  like  sample  C,  and  in  the 
same  conditions. 

When  other  samples,  A',  B',  C,  D',  E',  were 
impregnated  with  the  same  solutions,  but  after 
being  dried  were  passed  into  menstrua  containing 
either  bi-carbonate  of  potash  or  soda,  or  the  neu- 
tral arseniate  of  potash  and  a  little  chalk,  or  any 
other  saturating  body  incapable  by  its  nature  of 
redissolving  the  aluminous  compound  which  is 
formed ;  and  when,  as  in  the  preceding  case,  all 
the  samples  had  been  washed  and  passed  into  a 
madder  bath,  the  following  is  the  state  in  which 
they  presented  themselves : — 

Sample  A'  had  a  shade  of  a  much  higher  tone 
than  sample  A. 

Sample  B'  was  of  a  shade  double  the  intensity 
of  that  of  sample  B. 

Sample  C  of  the  same  shade  and  tone  as  sample  - 
A',  while  C  was  colorless,  or  very  slightly  tinted. 

Sample  D'  of  a  deeper  dye  than  D,  intermediate 
between  those  of  A'  and  B'. 

Sample  E';  instead  of  being  colorless  as  sample 


152 


ALUMINOUS  MORDANTS. 


E,  had  a  tint  the  intensity  of  which  was  propor- 
tional to  the  alumina  of  the  alum  which  was  fixed. 

Chloride  of  alumina  gives  the  same  results  as 
the  nitrate. 

Oxalate  of  alumina  presents  an  important  pe- 
culiarity, which  must  be  taken  into  consideration  ; 
at  the  moment  of  its  formation  it  has  not  the 
property  to  yield  its  basis  to  the  goods,  but  by 
prolonged  contact,  or  instantaneously  by  action  of 
the  steam,  this  salt  undergoes  a  transformation, 
and  giving  a  part  of  its  basis  to  the  goods,  becomes 
a  mordant. 

Alum  is  of  all  ingredients  the  most  generally 
employed,  and  that  which  has  been  longest  in 
use.  The  octahedral  alum  has  always  the  pro- 
perty of  yielding  to  the  stuff'  all  or  part  of  the 
alumina  it  contains,  when  it  has  been  previously 
saturated  with  acetate  of  lead,  lime,  baryta,  &c, 
which,  by  double  decomposition,  gives  sulphates 
more  or  less  soluble  and  a  proportionate  quan- 
tity of  acetate  of  alumina. 

Old  Mordants. 

Eed  mordant,  from  1760  to  1800.  In  22  gallons 
of  water,  they  dissolved, 

55.5  lbs.  alum,  to  which  they  add 


5.5  " 

arsenious  acid, 

5.5  " 

litharge, 

14.0  " 

acetate  of  lead, 

1.54  " 

sulphuret  of  antimony, 

1.54  " 

chloride  of  mercury, 

3.3  « 

carbonate  of  soda. 

ALUMINOUS  MORDANTS. 


153 


Other  from  1800  to  1824.  In  22  gallons  of  water, 
they  dissolved, 

49.5  lbs.  alum,  and  to  this  add 
5.0  "    acetate  of  copper,  previously  dissolved  in 
one  quart  of  acetic  acid, 
27.5  "    chlorhydrate  of  ammonia; 
24.2  "    carbonate  of  potash, 
24.2  "  "  lime, 

19.1  "    acetate  of  lead. 

New  Mordants. 
Mr.  D.  Koechlin,  in  his  memoir  on  red  mor- 
dants, gives  the  composition  of  the  three  fol- 
lowing:— 

Mordant  No.  1. 
In  22  gallons  of  water  dissolve  , 
88.0  lbs.  alum, 
8.8  "    carbonate  of  soda, 
88.0  a    acetate  of  lead. 

Mordant  No.  2. 
In  22  gallons  of  water  dissolve 
60.0  lbs.  alum, 

6.0  "    carbonate  of  soda, 
44.5  u    acetate  of  lead. 

Mordant  No.  3. 
In  22  gallons  of  water  dissolve 
44.5  lbs.  alum, 

5.0  "    carbonate  of  soda, 
29.7  "    acetate  of  lead. 


154 


ALUMINOUS  MORDANTS. 


The  following  is  the  process  to  prepare  these 
mordants : — 

In  a  tub  containing  the  powdered  alum,  pour 
the  quantity  of  warm  water  necessary  to  dissolve 
it,  then  add  the  carbonate  of  soda,  and  at  last  the 
acetate  of  lead.  A  precipitate  of  sulphate  of  lead 
is  formed.  Shake  the  whole  for  one  hour  without 
interruption,  and  afterwards  from  time  to  time 
only.  When  the  mordant  has  cooled  and  the  sul- 
phate of  lead  has  deposited,  decant  the  clear  liquor 
and  keep  it  in  stoneware  vessels. 

It  would  seem,  at  first  view,  that  in  all  estab- 
lishments, it  must  exist  a  mother  mordant  with 
which  all  the  others  might  be  prepared  by  diluting 
it  more  or  less  with  water,  and  making  additions 
to  it  of  substances  suitable  for  the  different  shades ; 
however,  it  is  not  the  custom  of  dyers  and  calico 
printers  who  prefer  to  prepare  several  kinds  of 
mordants,  being  guided  by  the  following  consider- 
ations : — 

1.  There  are  a  few  shades  for  which  a  very 
strong  mordant  is  required,  or  one  demanding  a 
greater  quantity  of  acetate  of  lead  than  a  mordant 
of  mean  density. 

2.  This  last,  into  the  preparation  of  which  less 
acetate  of  lead  enters,  keeps  longer  than  a  strong 
mordant,  which  soon,  by  decomposition  in  the 
cold,  depositing  more  subacetate  of  alumina  than 
the  mordant  of  mean  density,  would  not  always 
give  a  constant  result  when  diluted  with  water. 


ALUMINOUS  MORDANTS. 


155 


3.  A  strong  mordant,  in  which  the  acid  acetate 
predominates,  would  not  suit  in  several  styles  of 
printing,  especially  in  that  which  consists  of  two 
or  three  reds  where  mordants  of  different  density 
are  printed  one  on  another,  because  then  the  mor- 
dants getting  confounded  together  would  produce 
less  distinct  tints. 

4.  The  mode  of  giving  consistence  to  a  mordant, 
or  of  thickening,  varies  according  to  the  kind  of 
printing  for  which  it  is  intended,  and  an  acid 
mordant  cannot  be  inspissated  so  easily  as  another, 
with  any  of  the  substances  which  are  employed 
for  that  purpose. 

5.  A  strong  and  acid  mordant  is  less  easily 
discharged  by  the  operation  of  dunging. 

In  many  calico-printing  works  in  the  neighbor- 
hood of  Paris  and  Eouen,  they  use  for  the  prepa- 
ration of  the  red  mordants,  sulphate  of  alumina, 
which  is  now  manufactured  in  pretty  large  quan- 
tities.   As  it  occurs  in  commerce,  it  contains : — 

Centesimally. 

Sulphuric  acid  33.178 

Oxide  of  aluminum  ....  17.820 
Water   49.002 

100.000 

It  requires,  therefore,  seventy-five  parts  of 
acetate  of  lead  to  effect  its  partial  saturation,  and 
one  hundred  and  eighteen  parts  of  this  same  salt 
to  render  the  double  decomposition  complete,  and 
in  order  that  all  the  sulphuric  acid  may  be  pre- 


156 


ALUMINOUS  MORDANTS. 


cipitated  in  the  state  of  insoluble  sulphate  of  lead. 
Nevertheless,  these  proportions  of  acetate  may 
vary  considerably,  for,  as  has  been  already 
remarked,  the  composition  of  the  sulphate  of 
alumina  is  not  always  the  same.  It  is  certain 
that  the  commercial  article  contains  different 
quantities  of  acid  and  of  base,  and  the  manufac- 
turer cannot  exercise  too  much  circumspection  in 
the  use  of  this  salt,  especially  for  certain  kinds  of 
printing. 

M.  D.  Koechlin  prepares  the  red  mordant  with 
the  sulphate  of  alumina  by  operating  in  the  fol- 
lowing manner: — 

To  one  hundred  and  ten  parts  of  a  solution  of 
sulphate  of  alumina,  marking  52°  Twaddell  when 
it  is  hot,  and  56°  when  cold,  he  adds  one  hundred 
parts  of  acetate  of  lead  dissolved  in  thirty  parts  of 
water;  a  double  decomposition  takes  place  between 
these  two  salts,  and  a  solution  of  acetate  of  lead  is 
obtained,  marking  24°  to  26° — the  most  concen- 
trated which  can  be  obtained. 

There  are  print-works  in  which  the  acetate  is 
replaced  by  an  equal  weight  of  acetate  of  lead ; 
but  when  one  does  not  wish  to  use  either  the 
one  or  the  other,  equivalent  quantities  of  acetate 
of  lime,  baryta,  or  soda  may  be  substituted,  since 
2375  pounds  crystallized  acetate  of  lead  are  replaced  either 

by 

1600  pounds  anhydrous  acetate  of  baryta,  or  by 
1708  "  crystallized  acetate  of  soda,  or  by 
1233       "      anhydrous  acetate  of  potash 


ALUMINOUS  MORDANTS. 


157 


If  commerce  supplied  the  market  with  the 
acetates  of  baryta  or  lime  in  a  state  of  purity,  the 
manufacturer  would  find  a  great  advantage  in 
using  them,  because  he  would  leave  the  sulphate 
of  lime  or  of  baryta,  the  product  of  the  double 
decomposition,  mixed  with  the  mordant,  and  these 
salts  would  contribute  as  a  mastic  to  the  thickening 
of  the  color. 

Instead  of  making  the  mordants  by  the  way  of 
double  decomposition,  which  always  necessitates 
the  employment  of  an  acetate,  the  mordant  of  which 
M.  D.Kcechlin  indicated  the  preparation  has  long 
been  manufactured  on  the  large  scale,  and  the  fol- 
lowing is  the  process  employed:  1.  Neutralize  a 
solution  of  alum,  saturated  in  the  cold,  with  car- 
bonate of  potash,  which  is  added  by  degrees 
with  agitation,  till  the  flakes  which  are  formed 
begin  to  be  no  longer  redissolved.  2.  Bring  this 
neutralized  solution  to  the  boiling  point,  so  as  to 
cause  the  formation  of  basic  sulphate  of  alumina, 
which  is  collected  and  afterwards  treated  with 
acetic  acid,  wherein  it  dissolves  perfectly,  espe- 
cially in  the  heat,  furnishing  one  of  the  strongest 
and  most  reliable  mordants  that  can  be  prepared 
and  employed.  But  it  would  be  too  troublesome 
to  make  this  preparation  on  a  small  scale  and  in 
the  works  themselves,  since  it  would  be  necessary 
to  throw  away  the  water  from  which  the  basic 
sulphate  of  alumina  had  been  separated,  and  along 
with  this  water  the  sulphate  of  potash,  so  that  all 
14 


158 


ALUMINOUS  MORDANTS. 


the  potash  of  the  alum,  the  whole  of  that  which 
served  for  its  precipitation,  and  lastly,  a  certain 
quantity  of  the  alum  itself  would  be  lost.  If,  on 
the  contrary,  the  fabrication  of  this  product  were 
conducted  on  the  large  scale  in  an  alum  factory, 
where  the  water  more  or  less  saturated  with  sul- 
phate of  potash  might  enter  again  continually  into 
a  new  operation,  there  would  be  no  loss  of  alkali; 
the  basic  sulphate  of  alumina  produced  would  be 
constant  in  its  composition,  dissolving  well  in  the 
acetic  acid ;  and  in  this  case  one  would  economize 
the  whole  of  the  potash  of  the  alum,  which 
might  be  turned  to  good  account,  and  all  the 
oxide  of  lead,  when  the  acetate  of  this  base  was 
employed. 

Applications. — The  mordants  of  alumina  are 
employed  alone  or  with  some  other  mordants,  for 
the  fixation  of  all  coloring  matters,  which  require 
an  intermediate  agent  to  constitute  a  color,  and  to 
become  afterward  adherent  to  the  goods. 


FERRUGINOUS  MORDANTS.  159 


CHAPTER  XX. 

I      FERRUGINOUS  MORDANTS. 

The  ferruginous  preparations,  like  aluminous 
ones,  only  perform  the  part  of  mordants  so  far  as 
they  are  soluble,  and  cause  a  deposit  of  oxide  of 
iron  on  the  stuff*.  Iron  presents  several  degrees 
of  oxidation,  and  it  is  necessary  to  find,  not  only 
the  saline  combination  which  best  gives  up  its 
base  to  the  stuff,  but  further,  that  which  possesses, 
in  addition  to  this  property,  the  degree  of  oxida- 
tion necessary  to  attract  the  coloring  matters  with- 
out injuring  the  goods.  The  fact  must  not  be 
lost  sight  of,  that,  in  depositing  a  ferruginous 
preparation  on  the  goods,  the  iron  may  be  com- 
bined either  in  the  state  of  protoxide,  which 
passes  by  little  and  little  to  the  state  of  sesqui- 
oxide  and  even  of  ferroso-ferric  oxide — Te304; 
or  in  the  state  of  sesqui-oxide,  which  may  be  hy- 
drated,  namely,  in  that  in  which  it  preserves  its 
chemical  condition,  or  anhydrous,  exhibiting  that 
modification  in  which  it  is,  so  to  speak,  unfit  to 
perform  any  part ;  are  Jastly  in  the  state  of  a 
subsalt  or  insoluble  neutral  salt. 


160  FERRUGINOUS  MORDANTS. 


In  a  paper  entitled,  Employment  of  pyroligneous 
acid  in  some  operations  of  the  arts,  and  published  in 
the  Annates  des  arts  et  manufactures ,  M.  Bosc  exa- 
mines in  what  state  of  oxidation  iron  should  exist 
on  the  goods  to  serve  as  a  base  for  black.  Ac- 
cording to  this  author,  one  should  obtain  on 
cotton  a  deep  black  tint,  firm  and  brilliant,  only 
in  so  far  as  use  is  made  of  a  salt  of  iron  with  a 
base  of  black  or  protoxide,  and  the  most  favora- 
ble combination  would  result  from  the  solution  of 
the  iron  in  acetic  acid,  because  this  acid,  by  the 
carbon  which  it  contains,  would  prevent  oxida- 
tion, and  maintain  the  oxide  at  its  inferior  degree. 

Arriving  at  the  same  conclusions,  in  a  very 
extended  memoir  which  treats  of  the  fixation  of 
the  mordants  of  iron  on  cotton  goods,  M.  H. 
Schlumberger  establishes,  first,  that  the  acetate 
of  iron  obtained  by  several  processes  gives  re- 
sults very  similar,  and  bases  this  proposition  on 
the  following  experiments: — 

He  thickened  with  gum-water  on  the  one  hand, 
and  with  starch  on  the  other,  the  following  solu- 
tions of  equal  strength — 10°  Twaddell — videlicet, 

The  first,  pf  acetate  of  iron  obtained  by  the 
double  decomposition  of  sulphate  of  iron  and 
acetate  of  lead. 

The  second,  of  acetate  of  iron  produced  from  a 
solution  of  iron  in  acetic  acid. 

The  third,  of  acetate  of  iron  produced  by  a 
solution  of  the  metal  in  ordinary  vinegar. 


FERRUGINOUS  MORDANTS. 


161 


The  fourth,  of  acetate  of  iron  prepared  by  means 
of  partially  purified  pyroligneous  acid. 

The  fifth,  of  acetate  of  iron  from  which  the  tar 
had  been  separated  by  five  minutes'  boiling. 

The  sixth,  of  crude  acetate  of  iron  containing  a 
great  excess  of  tar. 

The  seventh,  and  last,  of  crude  acetate  of  iron 
mixed  with  the  purified  salt. 

These  compositions  were  printed  in  the  same 
conditions  on  pieces  of  calico ;  each  resulting  sam- 
ple was  then  divided  in  two,  and  exposed  to  the 
atmosphere,  one-half  for  two  days  only,  the  other 
for  ten,  before  being  submitted  to  the  operation 
of  dunging,  and  passed  into  a  madder-bath  where 
all  gave  a  very  fine  violet,  intense  and  very  rich. 

When  an  acetate  is  employed  as  a  mordant, 
theory  and  practice  direct  that  the  proto-acetate  of 
iron  be  applied,  in  preference  to  the  goods,  and 
this,  by  decomposing  on  the  stuff,  passes  by  slow 
degrees  to  the  state  of  a  basic  salt,  which  oxidizes 
in  the  air ;  and,  as  it  was  desirable  to  inquire  into 
the  circumstances  in  which  this  oxidation  might 
be  effected  without  danger  to  the  fabric,  M.  H. 
Schlumberger  turned  his  attention  to  the  question, 
and  relates  the  results  of  experiments  which  he 
made  on  the  four  ferruginous  preparations  which 
follow,  some  at  24°  Twaddell,  and  others  at  only 
7°. 

1.  Acetate  of  iron  obtained  directly  from  the 
solutions  of  iron  in  acetic  acid. 

14* 


162 


FERRUGINOUS  MORDANTS. 


2.  Crude  acetate  of  iron. 

3.  Acetate  of  iron  obtained  by  the  double 
decomposition  of  acetate  of  lead  and  sulphate  of 
iron. 

4.  The  same  solution,  but  with  an  excess  of 
acetate  of  lead  added. 

After  printing  these  different  solutions,  gum- 
med and  not  gummed,  on  as  many  samples  as 
were  necessary  to  study  the  different  circum- 
stances of  oxidation,  he  exposed  some,  in  a  place 
with  a  mean  temperature,  to  a  moist  air  and  dif- 
fused light ;  others  in  a  warm  situation,  dry  and 
darkened;  others  in  fine  to  the  rays  of  the  sun 
and  to  all  the  atmospheric  variations  ;  and  left  in 
these  different  conditions  the  half  of  each  of  these 
samples  for  six  days,  and  the  other  half  for 
twenty-one  days ;  then  he  passed  them  all  into 
dung,  to  be  subsequently  cleaned  and  dyed,  after 
which  he  found — 

1.  That  the  weakening  of  the  stuff  generally 
took  place  only  in  the  samples  on  which  the  con- 
centrated ferruginous  solutions  had  been  printed, 
and  that  in  one  case  only,  this  weakening  was 
remarked  on  the  stuffs  impregnated  with  a  solu- 
tion marking  6° ; 

2.  That  the  goods  were  weakened  by  any  of 
the  four  mordants  mentioned  above ;  less,  how- 
ever, with  the  last,  containing  an  excess  of  the 
acetate  of  lead ; 

3.  That  the  pure  mordants  weakened  the  stuff 


FERRUGINOUS  MORDANTS. 


163 


much  more  than  those  which  were  thickened  with 
gum,  starch,  or  fecula ; 

4.  That  exposure  to  the  solar  rays  promotes  in 
a  given  time  the  injurious  effect  on  the  goods,  to 
such  a  degree  that  weak  mordants,  which  do  not 
attack  the  calico  in  darkness  or  in  a  diffuse  light, 
deteriorate  it  very  powerfully  in  the  sun ; 

5.  That  in  all  the  cases  the  weakening  of  the 
fabric  does  not  decidedly  show  itself  till  the  third 
or  sixth  day,  but  that  at  this  period  it  is  nearly 
the  same  as  after  the  twenty -first  day  of  the  con- 
tact of  the  mordant  with  the  stuff ; 

6.  Lastly,  that  as  the  samples  are  passed  into 
the  dung  at  a  boiling  heat,  or  only  at  the  tempera- 
ture of  122°,  and  according  as,  on  taking  them 
out  of  this  bath,  they  are  or  are  not  dipped  into 
a  dilute  solution  of  chlor-oxide  of  calcium,  the 
deterioration  of  the  fabric  is  more  or  less  decided, 
that  is  to  say,  it  is  scarcely  perceptible  if  the 
samples  have  been  cleared  in  a  dung-bath  heated 
to  122°,  and  if  they  have  not  been  passed  into 
bleaching  powder  liquor;  and,  on  the  contrary, 
it  is  always  strongly  marked  when  the  same  sam- 
ples have  been  passed  into  the  dung  at  a  boiling 
temperature,  or  immersed  immediately  in  the 
chlor-oxide. 

After  having  thus  shown,  on  the  one  hand,  that 
this  weakening  of  the  fabric  is  due  to  the  oxida- 
tion which  takes  place  by  reason  of  the  quantity 
of  protoxide  which  is  deposited  upon  it,  and  on 


164  FERRUGINOUS  MORDANTS. 


the  other,  that  it  is  reduced  to  nothing  when  the 
mordants  are  weak,  and  is  very  marked  when 
they  are  concentrated,  M.  H.  Schlurnberger  ex- 
plains this  by  the  consecutive  effects  of  the  com- 
bination of  the  protoxide  with  the  fabric,  a 
circumstance  involving  disengagement  of  heat 
and  electricity.  M.  Persoz  accounts  for  this  phe- 
nomenon by  the  fact  of  the  momentary  production 
of  ferric  acid — Fe03 — which,  as  he  ascertained  by 
direct  experiment,  destroys  the  tissues  with  great 
energy  when  it  is  free  in  their  presence. 

It  appears,  from  the  researches  of  Schlurn- 
berger, that  if,  for  fast  impressions  in  black  or 
violet,  use  is  made  of  crude  acetate  of  iron 
strongly  charged  with  a  tar  which  obstinately 
maintains  the  iron  in  the  state  of  protoxide  on 
the  cloth,  very  bad  results  are  obtained  in  the 
dyeing,  whilst  the  same  salt  mixed  with  a  certain 
quantity  of  acetate,  prepared  by  the  solution  of 
iron  in  acetic  acid,  never  gives  any  but  good  re- 
sults. 

To  these  two  orders  of  facts — which  demon- 
strate, the  one,  the  inefficacy  of  a  mordant  too 
energetically  maintained  in  the  state  of  protosalt, 
the  other,  on  the  contrary,  the  efficacy  of  the 
mordant  which  is  capable  of  passing  to  a  superior 
degree  of  oxidation — Schlurnberger  adds  others, 
which  he  adduces  as  affording  unequivocal  proof 
that  a  too  advanced  oxidation  is  always  hurtful. 

Thus,  for  example,  after  having  steamed  samples 


FERRUGINOUS  MORDANTS.  165 


on  which  were  printed  mordants  of  violet  and 
puce-color — mixture  of  iron  and  alumina — he 
remarked  that  these  samples,  when  dyed  and 
heightened,  presented  shades  of  a  much  more 
reddish  tint  than  if  the  mordants  had  not  been 
submitted  to  the  action  of  the  steam,  which, 
nevertheless,  appeared  to  him  more  hurtful  to 
the  puce  mordants  containing  alumina,  than  to 
the  black  mordants  with  an  iron  base,  and  hence 
he  concluded  that  this  result  is  due  to  a  more 
advanced  oxidation ;  but  Persoz  thinks  that  there 
is  here  a  misapprehension  as  to  the  part  performed 
by  the  steam,  which  does  not,  in  his  opinion,  set 
up  any  phenomenon  of  oxidation,  but  simply  a 
change  of  physical  state  due  to  the  heat,  which 
renders  indifferent  a  certain  quantity  of  the  ox- 
ides of  iron  and  aluminum  that  are  fixed  on  the 
stuff,  and  produce  in  this  case,  mixed  with  the 
violet — the  sesqui-oxide,  a  kind  of  brown;  and 
alumina,  a  less  full  shade. 

Other  samples,  impregnated  in  like  manner 
with  mordants,  and  dipped,  some  into  a  solution 
of  bichromate  of  potash,  others  into  a  bath  of 
bleaching  powder  diluted  and  heated  to  104°,  did 
not  give  better  results ;  the  tints  of  the  samples 
passed  into  the  bichromate  were  even  more  red- 
dish than  those  of  the  specimens  passed  into  the 
steam,  which  may  be  accounted  for,  when  it  is 
borne  in  mind  that  always  when  a  stuff*  on  which 
a  protosalt  is  printed,  is  dipped  into  a  solution  of 


166  FERRUGINOUS  MORDANTS. 


bichromate  of  potassa,  there  is  a  double  decom- 
position, followed  by  deterioration,  and  conse- 
quently the  formation  of  a  compound  which  may 
be  represented  by  a  certain  quantity  of  sesqui- 
oxides  of  chrome  and  iron ;  now,  these  acting  as 
mordants,  and  the  former  producing  brown  shades, 
it  is  not  surprising  that  one  cannot  obtain  fine 
violets. 

As  for  the  action  of  the  chlor-oxide  of  calcium, 
it  is  very  simple :  it  modifies  the  physical  state  of 
the  sesqui-oxide  without  changing  its  composition. 

According  to  Mr.  Mercer,  the  best  iron  mor- 
dant is  the  crude  acetate — pyrolignite — properly 
made,  free  from  tar;  but  containing  all  the  ethereal 
oils  and  spirit,  as  also  the  deoxidizing  coloring 
matter,  which  prevent  the  too  rapid  oxidation  of 
the  iron.  This  mordant,  combined  with  a  proper 
quantity  of  white  arsenic — arsenious  acid — so  as 
to  form  sesqui-arsenite  of  iron  as  oxidation  pro- 
gresses and  acetic  acid  evaporates,  is  the  height 
of  perfection  for  lilacs  and  fine  plate  work.  The 
English  purple  plate  styles  from  this  mordant  are 
unequalled. 

To  sum  up,  it  may  be  affirmed,  without  fear  of 
contradiction  from  experiment,  that  when  solutions 
of  iron  obtained  by  acetic  acid  are  applied  on  the 
stuff,  with  the  view  of  making  them  perform  the 
part  of  mordants,  it  is  right  that  they  be  in  the 
state  of  protoxide,  in  order  that,  the  oxidation  tak- 
ing place  on  the  cloth,  there  may  be  formed  a  basic 


FERRUGINOUS  MORDANTS. 


167 


acetate  which  will  preserve  to  the  sesqui-oxide 
its  chemical  properties,  and  pass  to  the  state  of 
phosphate  or  arseniate  in  the  operation  of  dunging. 
It  is  necessary  that  this  oxidation  be  slow  and 
progressive,  for,  if  it  is  rapid,  the  risk  of  the  stuff 
being  deteriorated,  or  of  the  sesqui-oxide  passing  *» 
into  that  isomeric  state  in  which  it  becomes,  as  it 
were,  indifferent  to  chemical  agents,  is  incurred. 

As  for  the  other  ferruginous  compounds,  all 
the  acid  salts  are  unfit  to  perform  the  part  of  mor- 
dants, while  it  is  otherwise  with  the  neutral  salts, 
seeing  that  the  protoxide  which  they  contain, 
passing  to  the  state  of  sesqui-oxide  by  absorbing 
the  oxygen  of  the  air,  they  no  longer  contain 
enough  of  acid  to  form  a  neutral  salt,  and  con- 
sequently there  is  the  formation  of  a  basic  salt 
which  becomes  fixed  on  the  stuff.  It  is  thus  that 
one  explains  why  the  neutral  protosulphate  which 
remains  on  the  calico  yields  to  it  always  a  certain 
quantity  of  its  base,  whereas,  when  it  is  acid,  this 
phenomenon  no  longer  presents  itself.  As  for 
the  sesquisalts,  all  those  which,  from  any  cause 
whatever,  can  pass  into  the  state  of  basic  salts, 
then  become  true  mordants,  capable  of  attracting 
coloring  matters. 

When  the  iron  is  in  contact  with  the  calico  in 
presence  of  moist  air,  it  produces,  by  oxidizing, 
spots  of  rust,  which  become  fixed  on  the  cloth 
and  attract  the  coloring  matter. 

In  the  same  circumstances  the  protosulphate  pre- 


168 


FERRUGINOUS  MORDANTS. 


sents  the  same  results,  either,  from  the  circum- 
stances that,  passing  into  the  state  of  sulphate,  by 
an  absorption  of  oxygen,  it  is  immediately  trans- 
formed into  a  basic  salt  by  fixing  a  higher 
proportion  of  oxygen,  or  that  it  has  directly  the 
power  of  fixing  by  a  double  decomposition  a  certain 
quantity  of  coloring  matter. 

The  Alkaline  Mordants  of  Iron. — Few,  besides 
Haussmann,  have  employed  as  mordants  alkaline 
ferruginous  solutions.  He  dissolves  iron,  or  the 
protosulphate  gently  in  nitric  acid,  under  which 
condition  there  was  always  the  formation  of  an 
ammoniacal  salt.  The  following  directions  explain 
the  reaction. 

8Fe  +  19N05  +  4H0  =  5(Fe203,3N05)  +  NH,3N05H0  + 

Iron.    Nitric  acid.      Water.     Sesqui-nitrate  of  iron.    Nitrate  of  am- 
monia. 

NO*          +  NO 
V  ,  '     »  ,  1 

Bioxide  of  nitrogen.    Protoxide  nitrogen. 

The  liquor  abstracted  was  afterwards  saturated 
with  carbonate  of  potash,  which  was  poured  in 
very  cautiously.  The  precipitate  which  formed 
at  first  was  soon  redissolved  by  an  excess  of  car- 
bonate of  potash,  giving  rise  to  a  double  salt, 
which  was  decomposed  by  the  alkaline  oxide. 
Haussmann  states  that  he  uses  this  solution  with 
success  in  many  circumstances. 

Applications. — Those  mordants  are  used  alone 
or  mixed  with  those  of  alumina.  In  the  first  case 
they  serve  with  the  red  coloring  matters  to  pro- 


FERRUGINOUS  MORDANTS. 


169 


duce  on  the  stuffs  gray,  lilacs,  violets  and  blacks ; 
with  the  yellow  they  give  grays,  olives  more  or 
less  deep,  with  a  mixture  of  red  and  yellow,  a 
multitude  of  shades,  from  clear  gray  to  the  deepest 
black.  Associated  with  alumina  mordants,  the  fer- 
ruginous give  with  red  coloring  matters,  pure 
shades  more  or  less  intense ;  with  yellow,  yellows 
more  or  less  olive;  with  a  mixture  of  red  and 
yellow  they  give  brown  colors,  dead  leaves,  rather 
mauve,  &c,  which  vary  indefinitely  according  to 
the  respective  proportions  of  the  mordants  of 
alumina  and  iron. 


15 


170 


STANNIFEROUS  MORDANTS. 


CHAPTER  XXL 

STANNIFEROUS  MORDANTS. 

Tin,  by  uniting  with  oxygen,  gives  two  oxides, 
one  which  reacts  as  a  powerful  base,  the  other  as 
an  acid ;  both  are  applicable  as  mordants.  From 
all  metallic  compounds  the  stanniferous  combina- 
tions are  those  which  adhere  to  the  goods  with 
the  greatest  energy.  The  choice  between  a  stan- 
nous and  stannic  salt  is  determined  by  the  nature 
of  the  goods,  and  by  that  of  the  colors  that  it  is  de- 
sired to  fix  upon  them.  It  will  here  be  sufficient 
to  consider  the  conditions  in  which  these  com- 
pounds must  exist. 

The  compounds  in  which  the  oxide  of  tin  performs 
the  part  of  a  base  are  of  two  kinds ;  some  having  a 
base  of  protoxide,  and  others  of  binoxide.  The 
protoxide  is  the*  most  generally  used ;  it  cannot 
be  separated  on  the  stuff  without  giving  up  to  it 
a  certain  quantity  of  its  base,  seeing  that,  when 
treated  with  water,  it  undergoes  a  partial  decom- 
position, and  is  transferred  into  an  acid  salt, 
which  remains  in  solution  in  that  medium,  and 


STANNIFEROUS  MORDANTS.  171 


into  a  basic  insoluble  compound,  which  adheres 
to  the  fabric. 

Instead  of  chloride  of  tin,  Bancroft  employed 
a  solution  of  the  protosulphate  in  hydrochloric 
acid,  which  decomposes  more  easily  in  presence  of 
the  goods.  He  prepares  it  in  the  following  man- 
ner :  On  22  lbs.  of  granulated  tin,  introduced 
in  a  stoneware  vessel,  he  pours  36  lbs.  of  com- 
mercial hydrochloric  acid  free  from  iron,  adds 
little  by  little  to  this  mixture  16  J  lbs.  of  sulphuric 
acid ;  there  is  development  of  heat,  the  tin  is 
attacked  first  with  violence,  but  it  dissolves  more 
slowly  in  proportion  as  the  liquor  comes  more 
concentrated.  The  mixture  is  heated  in  a  sand 
bath  till  complete  dissolution.  The  whole  being 
left  to  cool,  a  saline  mass  is  obtained  which  con- 
tains a  slight  excess  of  tin.  The  liquor  is  de- 
canted, the  remaining  metal  is  weighed  to  know 
how  much  has  been  dissolved,  and  the  liquor  is 
diluted  with  as  much  water  that  its  weight  may 
be  eight  times  that  of  the  tin  dissolved ;  that  is  to 
say,  160  lbs.  for  example,  if  there  have  been  20 
lbs.  of  tin  dissolved.  Among  the  compounds  of 
binoxide  of  tin,  there  is  a  multitude  of  preparations 
which  are  employed  as  mordants  or  constituent 
parts  of  the  latter  which  are  applied  on  the  goods, 
and  which  contained  binoxide,  either  pure  or  mixed 
with  protoxide.  They  are  generally  called  Tin 
compositions.    The  following  are  some  of  them:— 


172  STANNIFEROUS  MORDANTS. 

1st.  22  lbs.  of  tin  in  ribands  are  dissolved  with 
precaution  in  a  mixture  of 
55  "    nitric  acid, 
120  "    commercial  hydrochloric  acid. 

2d.  22  u  granulated  tin  are.  dissolved  in  a 
mixture  formed  of 

44  "    hydrochloric  acid, 

44  "  nitric  acid  in  which  has  been  pre- 
viously dissolved 

11  "    hydrochlorate  of  ammonia. 

3d.  22  "  tin  in  ribands  are  gradually  dis- 
solved in 

176  u    nitric  acid  at  40°  in  which  has  been 
previously  dissolved 
22  a    chlorhydrate  of  ammonia. 

4th.  22  "  tin  are  dissolved  in 

22  "  nitric  acid  at  62°, 

44  a  hydrochloric  acid, 

44  "  water. 

5th.  22  "  protochloride  of  tin  are  dissolved  in 
a  mixture  of 

35  "  hydrochloric  acid  and 

17  J  "  nitric  acid; 

or  of 

17|  "  hydrochloric  acid  or 

15  "  nitric  acid  ; 
or  lastly  of 

11  u  hydrochloric  acid, 

15  "  nitric  acid. 


STANNIFEROUS  MORDANTS. 


173 


6th.    22.  lbs  protochloride  of  tin  are  gradually 
dissolved  in 
27|  "    nitric  acid. 
Further,  in  a  mixture  formed, 
7th.    22  lbs.  nitric  acid,  and 

22  11    hydrochloric  acid, 
as  much  tin  is  dissolved  as  these  acids  can  reduce, 
and  then  heat  is  applied  to  dissolve  in  this  liquor 
previously  decanted 

2.2  lbs.  protochloride  of  tin. 
8th.    22  "    tin  are  dissolved  with  caution  in 
42  "    nitric  acid  at  64°, 
33  "    hydrochloric  acid  at  36° ;  the  solu- 
tion being  effected,  add 
5  J  f<    acetate  of  lead. 

Lastly,  protochloride  of  tin  is  dissolved  by 
small  portions  at  a  time  to  the  point  of  saturation 
in  nitric  acid  at  66°  or  68°.  The  resulting  solu- 
tion has  the  consistence  of  a  jelly. 

With  reference  to  the  Compounds  in  which  Oxide  of 
Tin  performs  the  part  of  an  Acid, 

These  mordants  are  of  frequent  use ;  they  are 
prepared  by  dissolving  protoxide  of  tin,  or,  for 
greater  economy,  protochloride,  in  hydrate  of 
potash  or  soda.  These  bases  form  with  chlorine 
alkaline  chlorides,  and  the  stannous  acid  set  free, 
combines  with  the  excess  of  base  to  form  a  solu- 
ble stannite. 

This  compound  has  very  little  stability;  car- 
15* 


174 


STANNIFEROUS  MORDANTS. 


bonic  acid  of  the  air  tends  to  decompose  it,  and  an- 
other cause  is  the  unstability  of  its  molecules,  the 
atom  of  protoxide  is  divided  in  two  and  is  trans- 
formed in  binoxide,  and  metallic  tin  like  shows 
the  following  reaction : — 

2SnO  =  Sn02  +Sn 

Application  of  the  tin  mordants. — The  tin  mordants 
are  rarely  employed  to  obtain  dyed  colors  on  those 
called  maddered;  they  are  used  to  combat  the 
effects  of  iron,  or  after  the  dyeing  is  effected,  to 
transform  by  substitution  a  lake  with  a  base  of 
alumina  into  another  lake  with  a  stanniferous  lake. 
These  mordants  figure  in  all  the  colors  of  applica- 
tion, and  specially  in  steam  colors. 

Other  mordants  are  used  to  fix  colors  on 
fabrics  as  compounds  with  a  base  of  sesqui- 
oxide  of  chrome.  But  although  the  latter  oxide 
is  isomorphous  with  alumina,  and  sesquioxide  of 
iron  is  susceptible  of  adhering  to  the  goods,  and 
attracting  coloring  matters,  it  gives  rise,  by  its 
greenish  gray  shade,  to  lakes  which  are  not  clear 
in  the  colors. 

These  compounds,  as  well  as  those  of  some 
other  metallic  oxides,  not  being  in  general  use, 
do  not  require  to  be  minutely  discussed,  and  with 
reference  to  the  fatty  organic  mordant  which  plays 
so  important  a  part  in  the  Turkey  red,  we  refer  to 
general  works  on  the  art  of  dyeing  and  calico 
printing. 


ARTIFICIAL  ALIZARIN. 


175 


CHAPTER  XXII. 

ARTIFICIAL  ALIZARIN. 

We  have  seen  that  the  bi-nitro-naphthaline  is  a 
fecund  spring  of  colored  products;  the  action  of  re- 
ducing agents,  such  as  the  sulphurets,  the  stan- 
nous salts  dissolved  in  caustic  potash,  the  cyanide  of 
potassium,  &c,  give  with  this  substance  derivated 
products  which  are  red,  violet,  blue  and  very  rich. 
When  the  reducing  agents  are  of  an  acid  nature, 
such  as  a  mixture  of  zinc  and  diluted  sulphuric 
acid,  iron  filings  and  acetic  acid,  the  bi-nitro-naph- 
thaline is  not  alterated. 

If  you  make  to  act  concentrated  sulphuric  acid 
on  the  crystallized  bi-nitro-naphthaline,  it  is  no 
chemical  reaction.  In  heating  the  mixture  at 
482°  the  bi-nitro-naphthaline  is  dissolved,  and  sul- 
phuric acid  begins  to  act  only  after  a  long  ebulli- 
tion. When  this  solution  is  diluted  with  water,  the 
bi-nitro-naphthaline  is  precipitated  unalterated; 
the  same  if  you  treat  madder  at  212°,  by  con- 
centrated sulphuric  acid  all  the  products  are 
destroyed  but  one — the  coloring  principle — or 
alizarine. 


176 


ARTIFICIAL  ALIZARIN. 


The  formula  of  alizarine  is  represented  by — 

C20H6O6 

that  of  the  bi-nitro-naphthaline  by — 

C20H6(NO4)2 

A  reducing  agent  capable  to  take  two  molecules 
of  oxygen,  and  change  the  nitrogen  in  ammonia, 
could  probably  change  the  bi-nitro-naphthaline  in 
alizarine,  and  the  experiment  has  confirmed  that 
theory.  The  following  process  permits  to  prepare 
artificial  alizarine:— 

Make  a  mixture  of  bi-nitro-naphthaline  and 
concentrated  sulphuric  acid,  that  you  introduce  in 
a  large  dish  heated  in  a  sand  bath.  By  the  action 
of  heat  the  bi-nitro-naphthaline  is  dissolved  in  sul- 
phuric acid.  When  the  temperature  is  at  about 
392°,  throw  in  it  some  small  pieces  of  zinc;  few 
minutes  after  it  disengages  sulphurous  acid ;  half  an 
hour  after  the  operation  is  achieved.  If  you  let  fall 
a  drop  of  the  acid  mixture  in  cold  water,  a  mag- 
nificent red  violet  color  is  formed,  due  to  the 
formation  of  artificial  alizarine;  sometimes  the 
reaction  is  very  energetic ;  if  the  quantity  of  zinc 
is  too  considerable,  the  sulphuric  acid  boils  rapidly, 
and  a  large  quantity  of  white  vapors  are  disen- 
gaged. The  zinc  must  be  added  by  small  portions 
at  a  time. 

When  the  reaction  is  achieved,  dilute  the  liquid 
with  eight  or  ten  times  its  volume  of  water,  and 
boil,  few  minutes  after  you  filter.    The  artificial 


ARTIFICIAL  ALIZARIN. 


177 


alizarine  deposit  on  form  of  a  red  jell.  The  other 
water  is  strongly  colored  in  red,  and  contains  a 
considerable  quantity  of  alizarine  in  solution. 
This  water  can  be  used  directly  to  dye. 

In  the  preceding  reaction  the  zinc  can  be  sub- 
stituted by  many  other  substances,  such  as  tin, 
iron,  mercury,  sulphur,  carbon,  &c.  The  two 
following  equations  show  the  reaction : — 

C20H6(NO4)2  +  12M  +  18S03,H0  =  C20H5O6  +  2(S03NH3H0)* 

Bi-nitro-naph-  Alizarine.     Sulphate  of  am- 

thaline.  monia. 

+     12SCMO    +  10HO  +  4S02 

Metallic  Sulphate. 
C20H<3(NO4)2  +  IOC  +  14(S03H0)=  CW  + 


Bi-nitro-naphthaline.  Alizarine. 
2(S03,NH3H0)  +  10CO*  +  12  So2  -fc  6H0 

In  the  first  equation  it  is  the  metal  which  acts 
on  sulphuric  acid,  in  the  second  it  is  the  carbon 
itself. 

This  artificial  alizarine  has  all  the  characters 
of  the  ordinary  alizarine.  The  following  table 
shows  how  the  two  coloring  matters  comport: — 


178     METALLIC  HYPOSULPHITES  AS  MORDANTS. 


COLORING  MATTER  OF  THE 
MADDER 

is  precipitated  in  jell  from  its 
solutions, 

is  sublimated  between  4190 
and  464o. 

Little  soluble  in  water,  solu- 
ble in  alcohol,  ether,  and  a 
solution  of  alum, 

unalterable  by  sulphuric  acid 
heated  at  3920,  hydrochloric 
acid;  alterable  by  nitric  acid, 

soluble  in  caustic  or  carbonat- 
ed alkalies  with  a  purple 
color. 

The  ammoniacal  solution  gives 
purple  precipitates  with  the 
salts  of  baryta  and  lime. 


ARTIFICIAL 
RED  MATTER 

is  precipitated  in  jell  from  its 
solutions, 

is  sublimated  between  419° 
and  464o. 

Little  soluble  in  water,  solu- 
ble in  alcohol,  ether,  and  a 
solution  of  alum, 

unalterable  by  sulphuric  acid 
heated  at  3920?  hydrochloric 
acid;  alterable  by  nitric  acid, 

soluble  in  caustic  and  carbo- 
nated alkalies  with  a  blue 
violet  color. 

The  ammoniacal  solutions  give 
purple  precipitates  with  the 
salts  of  baryta  and  lime. 


The  elementary  analysis  gives — 

Carbon       .       .  63.26      .       .  63.51 
Hydrogen  .       .    2.10      .       .  2.30 
New  studies  deserve  to  be  done  on  this  inte- 
resting body,  which  is  called  to  render  important 
services  in  the  arts  of  dyeing  and  calico  printing. 

This  new'  substance  gives  colors  as  good  and 
solid  as  the  carmine  of  madder  for  impression  and 
fixation  of  colors  by  steam  on  mordanted  cotton 
cloths. 


METALLIC  HYPOSULPHITES  AS  MORDANTS.  179 


CHAPTER  XXIII. 

METALLIC  HYPOSULPHITES  AS  MORDANTS— DYER?S 
SOAP  —  PREPARATION  OF  INDIGO  FOR  DYEING 
AND  PRINTING — RELATIVE  VALUE  OF  INDIGO — 
CHINESE  GREEN — MUREXIDE. 

Mr.  E.  Kopp,  a  short  time  ago,  has  introduced 
the  use  of  metallic  hyposulphites  as  mordants, 
and  he  has  shown  that  their  use  is  preferable  to 
the  acetate  of  the  same  base.  The  hyposulphite 
of  lime  is  the  one  used  to  obtain  the  others,  its 
fabrication  is  known  by  every  chemist. 

Hyposulphite  of  Alumina. 

To  prepare  a  solution  of  hyposulphite  of  alumina 
he  decomposes  64.60  grains  of  sulphate  of  alu- 
mina (3(S03)AP03+18HO),  dissolves  in  water  by 
75.66  grains  of  crystallized  hyposulphite  of  lime; 
he  filters  and  expresses  the  residue  of  sulphate 
of  lime.  The  solution  is  clear,  limpid,  and  kept 
very  well  to  the  air ;  a  solution  of  hyposulphite 
of  alumina  marking  1.20  contains  as  much  alu- 
mina as  a  solution  of  acetate  of  alumina  at  1.10 
of  specific  gravity.  This  solution  can  be  thick- 
ened by  gum,  roasted  starch,  &c. 


180     METALLIC  HYPOSULPHITES  AS  MORDANTS. 


If  you  use  alum,  you  find  that  13  J  lbs.  of  alum 
are  decomposed  completely  by  9  lbs.  2  ounces  of 
hyposulphite  of  soda  (S202NaO  +  5HO),  or  by  9 
lbs.  3  ounces  of  crystallized  hyposulphite  of  lime 
(S202CaO  +  6HO).  It  follows  that  4 J  lbs.  of  this 
last  salt  can  take  the  place  of  6  lbs.  12  ounces  of 
acetate  of  lead. 

Hyposulphite  of  Protoxide  of  Iron. 

This  salt  can  be  obtained  by  the  action  of  sul- 
phurous acid  on  protosulphuret  of  iron  mixed  with 
water,  or  by  the  decomposition  of  the  protosulphate 
of  iron  by  the  hyposulphite  of  lime ;  it  must  be  kept 
out  of  the  contact  of  the  air.  In  dyeing  it  be- 
haves like  the  other  iron  mordants. 

Hyposulphite  of  Chrome.  x 

This  salt  is  prepared  like  the  corresponding 
salt  of  alumina.  It  must  be  prepared  a  short 
time  before  its  use. 

Hyposulphite  of  Tin. 

All  stannous  salts  being  acids  when  they  are 
mixed  with  an  alkaline  hyposulphite,  they  disen- 
gage hyposulphurous  acid.  With  the  salts  of  prot- 
oxide of  tin,  they  form  a  stannous  sulphuret  or 
oxy-sulphuret  which  are  precipitated  with  stan- 
noso-stannic ;  this  formation  takes  a  certain  time 
according  to  the  concentration  of  the  liquors. 


SOAP  FOR  DYERS. 


181 


In  using  a  salt  of  peroxide  of  tin,  it  is  no  precipi- 
tation of  tin  in  the  liquors.  The  above  observation 
shows  that  in  using  hyposulphites,  you  must  avoid 
mixing  with  a  stannous  salt,  but  always  use  a 
stannic  salt  or  a  mixture  of  them  both. 
This  salt  gives  a  very  good  mordant. 


Dyers  add  to  it  from  5  to  6  quarts  of  lye  of  potash 
at  5°,  and  18  to  20  quarts  of  lye  at  22°.  The 
coction  of  the  soap  lasts  twelve  hours. 


SOAP  FOR  DYERS. 


This  soap  is  composed  of — 
Ordinary  oil  or  fatty  body 
Palm  oil  . 
Spirit  of  Turpentine 


.  180  lbs. 
.  33f" 


In  all 


225  " 


16 


182  PEEP  A  RATION  OF  INDIGO  FOK 

PREPARATION  OF  INDIGO  FOR  DYEING  AND 
CALICO  PRINTING. 

Take  2  qts.  of  a  paste  containing  about  2  lbs. 
of  indigo  in  fine  powder,  mix  with  it  2  qts.  of 
glucose  prepared  with  rice  starch.  Take  after- 
wards 2 J  lbs.  of  slacked  lime  diluted  with  water, 
that  you  mix  with  the  glucose  and  indigo,  add 
then  2  lbs.  of  solid  caustic  soda  and  shake  care- 
fully. This  compound  thus  prepared  is  ready 
for  impression  which  is  executed  by  the  ordinary 
process.  To  dye  with  this  indigo  mix  together  the 
materials,  viz :  indigo,  glucose,  lime,  soda,  let  it 
work  a  certain  length  of  time  at  the  ordinary  tem- 
perature, and  introduce  it  in  the  vat  ready  for  the 
dyeing. 


Relative  value  of  indigo. 


Relative  value 

Ashes 

Water 

Country. 

in  coloring 

in  100 

in  100 

matter. 

parts. 

parts. 

Indigo  of  East  India 

.  68. 

4.5 

5.0 

a 

a 

.  66. 

5.8 

6.0 

tt 

u 

.  64. 

8.1 

8.0 

a 

a 

.  54. 

11.0 

7.0 

a 

a 

.  51.5 

7.2 

7.5 

n 

a 

.  54. 

3.6 

7.0 

a 

tt 

.  45. 

14.0  , 

8.4 

Spanish  Indigo 

.  55. 

12.3 

6.0 

a 

a 

.  50. 

13.0 

7.0 

a 

a 

.  44.5 

19.0 

5.5 

a 

a 

.  28. 

33.4 

4.5 

Bengal 

.  64. 

5.9 

4.0 

ii 

.  47. 

24.6 

5.0 

DYEING  AND  CALICO  PRINTING. 


183 


Benares 

.  45. 

20.7 

8.4 

Guatemala 

.  50. 

16.0 

6.5 

Madras 

.  41. 

10.6 

6.7 

Oude 

.  46. 

6.3 

8.5 

Caraccas 

.  52.5 

16.2 

6.4 

Madras 

.  35. 

33.3 

6.0 

Java 

.  63.5 

5.4 

4.8 

Bengal 

.  59.5 

7.5 

5.0 

CI 

.  56. 

11.0 

5.3 

a 

.  45.5 

14.0 

7.2 

a 

.  24. 

44.0 

4.4 

Manille 

.  35.5 

28.0 

5.0 

China  Green. 

Mr.  Charvin  has  extracted  from  the  Rhamnus 
catharticus  a  green  coloring  matter  similar  to  the 
Chinese  green  (green  indigo)  but  less  costly. 
This  product  is  in  irregular  plates  with  a  variable 
aspect,  according  to  the  thickness  of  the  plate. 
Like  the  Chinese  Lo-Kao  this  product  seems  to 
be  a  lake,  that  is,  a  combination  of  an  organic 
substance  with  an  earthy  matter.  Gradually  heated, 
it  lost  first  water  without  any  sublimate  product ; 
in  burning,  it  left  a  considerable  quantity  of  ashes. 
The  following  is  the  result  of  a  comparative  ex- 
periment done  at  the  same  time  with  that  product 
and  the  lo-Kao,  with  the  analysis  of  Mr.  Persoz  : — 


Green.  Charvin. 

Chinese. 

Chinese 

by  Persoz. 

Water 

13.5 

9.5 

9.3 

Ashes 

33. 

28.5 

28.8 

Coloring  matter 

53.5 

62. 

61.9 

100.0 

100.0 

100.0 

184  PREPARATION  OF  INDIGO  FOR 


Mr.  Persoz  defines  the  lo-Kao  "a  lake  formed 
by  cyanine,  having  for  base  phosphated  magnesia, 
alumina,  and  oxide  of  iron."  In  Mr.  Charvin's 
process,  lime  is  only  found,  mixed  with  a  little 
alumina  and  silica  without  phosphoric  acid,  but 
the  coloring  matter  is  the  same  in  the  two  pro- 
ducts. The  chemical  reactions  of  Mr.  Charvin's 
green  are  similar  to  the  Chinese  lo-Kao. 

Preparation. — In  a  kettle  containing  boiling 
water  he  puts  2  pounds  of  Rhamnus  caiharticus 
bark;  a  few  minutes  after  a  pink  skim  is  produced. 
He  then  puts  the  whole  into  an  earthen  jar,  well 
covered,  and  then  allows  it  to  rest  till  next  day. 
The  liquid  is  yellowish ;  it  is  decanted  and  lime 
water  added  to  it,  which  produces  a  change  of 
color ;  it  turns  reddish-brown,  the  liquid  is  put  in 
jars — very  little  in  each  one — and  the  whole  is  ex- 
posed to  air  and  light.  The  reddish-yellow  color 
is  modified  and  takes  a  green  shade;  little  by  little 
the  green  color  becomes  more  general,  and  is  then 
deposited  in  plates.  All  the  liquids  are  mixed 
together  and  carbonate  of  potash  is  added ;  a 
green  precipitate  is  produced;  he  leaves  it  to  de- 
posit, decants  the  liquid  and  collects  the  precipi- 
tate and  dries  it.  The  experiments  of  Mr.  Char- 
vin  prove, 

1st.  That  his  green  coloring  matter  is  of  the 
same  nature  as  the  Chinese  lo-Kao,  and  will  dye 
silk  in  as  beautiful  a  green  as  the  lo-Kao. 


DYEING  AND  CALICO  PRINTING. 


185 


2d.  This  matter  is  extracted  from  an  indige- 
nous plant,  the  Rhamnus  catharticus. 

3d.  That  the  process  will  permit  to  manufac- 
ture it  for  dyers  at  the  price  of  $8.90  per  pound. 

MUREXIDE. 

Murexide  can  be  manufactured  with  guano  or 
uric  acid,  the  processes  are  different. 

Fabrication  with  Guano. 

The  choice  of  a  good  guano  is  important,  the 
one  containing  the  most  urate  of  ammonia  is 
the  best.  In  the  best  Peruvian  guano  we  found 
at  least  5  and  the  most  15  per  cent,  of  uric  acid. 

1.  Treat  the  guano  by  hydrochloric  acid  to  de- 
compose the  carbonate  and  oxalate  of  ammonia, 
the  carbonate  and  phosphate  of  lime,  the  phos- 
phates of  ammonia  and  magnesia.  This  operation 
is  done  in  a  lead  kettle.  You  heat  the  acid  which 
marks  12°  B.  and  you  throw  in  it  gradually  the 
guano  by  small  portions. 

2.  Boil  the  mixture  one  hour,  draw  the  liquid 
in  wooden  vessels,  wash  the  deposit  by  decanta- 
tion. 

3.  The  guano  after  this  treatment  is  thrown  on 
large  filters ;  the  product  thus  obtained  contains 
from  42  to  45  per  cent,  of  dry  substance. 

4.  Tt  is  in  this  product  that  exists  the  uric  acid 

16* 


186  PREPARATION  OF  INDIGO  FOR 


mixed  with  sand,  gypsum,  organic  deposits,  and 
extractive  matters. 

5.  In  a  porcelain  dish  put  6  pounds  of  this 
guano  thus  prepared  with  1J  pound  of  hydro- 
chloric acid  at  24°  B.,  carry  the  whole  at  122°. 
Take  the  dish  from  the  fire  and  pour  in  it  little  by 
little  in  shaking  all  time  7  ounces  of  nitric  acid 
at  40°  B.;  be  careful  that  the  temperature  does 
not  rise  above  143°  and  fall  below  111°. 

6.  The  mixture  is  then  diluted  with  an  equal 
volume  of  water  and  filtered,  wash  the  deposit  with 
water,  reunite  all  the  solutions  and  precipitate  by 
a  saturated  solution  of  chloride  of  tin. 

7.  When  the  precipitate  is  well  formed,  decant 
the  brown  liquid  and  wash  it  with  water  containing 
hydrochloric  acid. 

8.  Throw  the  precipitate  on  a  filter,  dry  it  and 
expose  it  to  vapors  of  ammonia  which  transform 
it  into  murexide. 

Preparation  of  Uric  Acid  contained  in  Guano. 

The  guano  is  treated  by  hydrochloric  acid  as 
we  have  seen  above. 

In  a  copper  kettle  of  about  125  gallons  put  96 
gallons  of  water,  10  lbs.  of  caustic  soda,  and  the 
mass  obtained  by  the  treatment  of  252  lbs.  of 
guano  by  hydrochloric  acid  and  well  washed  with* 
water. 

Heat  the  mixture  till  boiling,  shake  all  time 
and  kept  at  this  temperature  for  one  hour. 


Add  to  it  a  milk  formed  with  2|  lbs.  or  3J  lbs. 
of  caustic  lime,  shake  well,  boil  J  of  an  hour,  take 
the  kettle  from  the  fire  and  let  it  settle  for  3  or 
4  hours. 

Decant,  and  in  the  clear  liquid  put  some  hydro- 
chloric acid  to  precipitate  the  uric  acid.  Wash 
this  precipitate  by  decantation,  collect  it  on  a  filter 
and  dry  it. 

When  you  have  taken  all  the  clear  liquid  from 
the  kettle,  put  on  the  residue  a  quantity  of  water 
equal  to  the  first  used,  add  again  from  to  7f 
lbs.  of  caustic  soda ;  operate  as  above  except  that 
for  the  clarification  you  use  only  from  19  ounces 
to  1J  lb.  of  lime. 

After  this  second  treatment  the  guano  is  gene- 
rally free  of  uric  acid ;  however,  it  is  good  and  safe 
to  repeat  the  operation  a  third  time  with  less  soda 
and  lime. 

The  uric  acid,  such  as  it  is,  can  be  used  immedi- 
ately to  prepare  Murexide. 

Fabrication  of  Murexide  after  the  Extraction  of 
Uric  Acid. 

For  2  lbs.  of  uric  acid  you  must  use  2  lbs.  10 
ounces  of  nitric  acid  at  36°  B. 

The  acid  is  put  in  a  dish  which  is  kept  in  cold 
water ;  then  you  throw  the  uric  acid  by  portions 
in  the  nitric  acid;  the  dose  must  not  exceed  one 
ounce  at  a  time ;  you  must  distribute  all  the  uric 
acid  in  the  mass  with  a  porcelain  spatula,  and  you 


188  PREPARATION  OF  INDIGO  FOR 

must  not  add  uric  acid  till  the  mixture  has  come 
at  80°. 

When  all  the  uric  acid  has  been  added,  you  let 
cool,  and  then  you  heat  the  whole  slowly  in  a  sand 
bath;  when  the  liquid  begins  to  swell  take  out 
from  the  fire,  and  when  the  swelling  has  fallen  back 
begin  again.  "When  you  heat  for  the  third  time, 
raise  the  temperature  at  230°,  and  then  put  in  the 
bath  9  J  ounces  of  liquid  ammonia  at  24°B.,  which 
transforms  the  mixture  into  murexide.  Leave  the 
dish  about  2  minutes  on  the  sand  bath,  take  it  out 
and  leave  to  cool;  you  found  a  kind  of  paste  in 
the  mixture  which  is  known  by  the  name  of 
murexide  in  paste. 

To  obtain  it  dry  and  pure,  mix  that  paste  with 
water,  filter  and  wash  well ;  the  last  washing  must 
be  done  with  ammonia  diluted  with  water;  dry  in 
the  oven  the  product  left  on  the  filter — it  is  the 
Dry  murexide. 

Application. — Murexide  can  be  applied  for  calico 
printing  in  powder  or  in  paste. 

Impression  with  the  Color. — In  9  gallons  of  boiling 
water  dissolve  25J  lbs.  of  crystallized  nitrate  of 
lead,  let  cool  the  liquid  till  144°;  dissolve  first 
in  it  5  lbs.  of  powdered  murexide  or  15  lbs.  of 
murexide  in  paste,  then  39  lbs.  of  powdered  gum; 
when  all  is  cold  it  can  be  used.  The  printing 
terminated,  hang  the  stuffs  in  a  damp  place  and 
you  fix  the  purple  by  ammoniac  gas,  the  same 
process  you  pass  woollen  stuffs  to  sulphurous  acid. 


DYEING  AND  CALICO  PRINTING.  189 


Passage  of  the  Stuffs  in  the  Bath  of  Sublimate. — 
The  warm  bath  in  which  the  tissues  are  passed 
after  exposition  to  the  ammoniacal  gas  is  composed 
of  191  gals,  of  water  and  2  lbs.  11  ounces  of  corro- 
sive sublimate.  The  tissues  are  passed  in  this  bath 
and  then  in  running  water,  then  they  receive  the 
bath  of  acetate  of  soda. 

Acetate  of  Soda. — This  bath  is  composed  of  360 
gals,  of  water  with  1  lb.  of  acetate  of  soda  and 
1  lb.  of  chlorhydrate  of  ammonia ;  the  tissues  are 
passed  in  for  20  minutes,  then  well  washed  and 
dried. 

This  progress  gives  a  very  beautiful  purple  red, 
all  the  gradations  of  red  and  rose  can  be  obtained 
with  murexide — the  colors  obtained  are  very 
solid. 


INDEX. 


A 

PAGE 

Aluming   44 

Aniline,  history  of  .       .  .      .  .60 

properties  of  60,  61 

direct  preparation  of      ....      60,  64 

artificial  preparation  of  68 

di-nitro  99 

green  88 

purple  81 

to  dye  with  113 

green,  to  fabrics,  method  of  application  of     .  118 

oxalate  .       .  .67 

Allyle-toluidine  82 

Art  of  dyeing,  historical  notice  of  the     ...  25 
chemical  principles  of  the      ....  33 

Azuline  110 

Alkaline  mordants  of  iron  168 

Alizarin,  artificial  175 

Alumina,  hyposulphite  of  179 

Acetate  of  soda  188 

B 

Benzole,  preparation  of   68,  69 

properties  of   68,  71 

properties  of  the  bi-nitro      .       .       .  68,  73 

bi-nitro   .  74 


192 


INDEX. 


PAGE 

Bleaching  silk  37 

cotton  39 

Bleu  de  Paris  89 

Benzolic  acid,  sulpho-  72 

Boiling  cotton  40 

silk  37,  38 

Bath  of  sublimate,  passage  of  stuff  in  189 

C 

Oarminaphtha  106 

Chloroxynaphthalate  of  ammonia  ....  105 
Calico  with  coal  tar  colors,  printing  ....  116 

Chloroxynaphthalic  acid  104 

Coal  tar,  on  the  coloring  matters  produced  by  .  .49 
history  of  the  coloring  matters  produced  by  .  49 

distillation  52 

to  the  arts  of  dyeing  and  calico  printing,  appli- 
cation of  ,  .112 

colors,  printing  with  116 

Chloraniline,  tri-  62 

Chlorophenic  acid,  tri-  62 

Chloranile  .........  62 

Cotton  33 

Cotton  with  colors  of  coal  tar,  to  dye  .  .  .  114 
Cotton  with  molybdic  acid,  to  dye     .      .      ,  .129 

Crysammic  acid  125 

preparation  125 

Cumidine    .       .       .       .  ,     .       .    .  .       .       65,  98 

Chrome,  hyposulphite  of  180 

China  green  183 

D 

Distillation  and  rectification  of  coal  tar,  table  of  the 

products  obtained  by  the  55 

Dyeing  47 


INDEX. 


193 


E 

PAGE 

Emcraldine       ....       .       .       .       .  88 

F 

Fibres,  preparation  of  the  textile  .  .  .  .33 
Fixation  of  coloring  matters  in  dyeing  and  printing, 

theory  of  the  .   133 

Futschine  .      -.      .       .       .       .       ...  92 

by  action  of  bichloride  of  tin  on  aniline,  pre- 
paration of  .       .       .       .       .       .       .  93 

by  action  of  nitrate  of  mercury,  preparation  of  94 

(t 

Guano,  preparation  of  uric  acid  in     ...  186 

[  .  H 

Hyposulphite,  metallic,  as  mordants  ....  179 

of  alumina      .       .  '   179 

of  protoxide  of  iron   180 

of  chrome   180' 

of  tin   180 

I 

Iodaniline   .       .  .97 

Improvements  in  the  art  of  dyeing    .       .       .       .  125 

Iron,  the  alkaline  mordants  of   .       .       .       .       .  168 

Indigo,  preparation  of,  for  dyeing  and  calico  printing  182 

relative  value  of      .      .      .      .      .      .  182 

L 

Light  on  coloring  matters  from  coal  tar,  action  of    .  120 

Lutidine    .       .       .       .       .       .       .       .       .  65 

17 


194 


INDEX. 


M 

PAGE 

Madder   130 

extract  of  130,  131 

Magenta   92 

Molybdic  acid   127 

Mordants   43 

aluminous       .       .       .       .       .       .       .  148 

old   152 

new                                                        .  153 

ferruginous   159 

principles  of  the  action  of  the  most  important  144 

stanniferous   170 

Metallic  hyposulphites  as  mordants  ....  179 

Murexide                                            .       .       .  185 

fabrication  of,  after  extraction  of    .       .       .  185 

Uric  acid   185 

application  of   185 

N 

Naphthamein  .109 

Nitro-phenisic  acid,  tri-  *  64 

Nitro-benzole,  preparation   68 

properties  68,  73 

into  aniline,  transformation  of  .  .  .  .68 
by  sulphide  of  ammonium,  reduction  of  .  .76 
by  nascent  hydrogen,  reduction  of  .  .  .77 
by  acetate  of  iron,  reduction  of      .       .  .79 

Nitro-azo-phenylamine  99 

Ninaphthalamine  106 

Nitroso-phenyline  98 

Nitro-phenyline  diamine  99 

Nitroso-naphthaline  107 

application  of  118 

Nitroso-phenyline  74 


INDEX.  195 
P 

PAGE 

Perchloroxynaphthalic  acid  104 

Picric  acid   64,  99,  127,  129 

Picoline  65 

Preparation  of  nitro-benzolc  73 

of  binitro-benzole  73 

of  futschine  93,  94 

Pyrrol       .       .       .  65 

Pyrrhidine  65 

Protoxide  of  iron,  hyposulphite  of    .       .       .       .  180 

Q 

Quinoline   65 

B 

Eed,  tar   110 

Roseine   87 

to  dye  with      .       .       .       .       .       .       .  113 

Rosolic  acid   101 

Scouring  wool  35 

Silk  37 

Silk  37 

Silk  and  wool  with  coal  tar  colors,  dyeing  .       .       .  112 
with  futschine,  picric  acid,  chinoline  blue  and 

violet,  to  dye  113 

with  azuline,  to  dye  .114 

with  molybdic  acid,  to  dye      .       .       .  .128 

Singing  cotton  stuffs  .       .       .       .       .       .  .39 

Stuffs,  preliminary  preparations  of    .       .       .  .39 

Stannous  salt  170 

Stannic  salt       .   -  170 

Soap  for  dyers  181 

Sublimate,  passage  of  stu  ns  in  bath  of  .  .  .189 
Soda,  acetate  of  .  189 


rs6 


TNDKX, 


T 

PAGE 

Tar  red  .      .       .  110 

Transformation  of  nitro-benzine  into  aniline      .      .  76 
Toluidine   ........      65,  98 

Tin    ..........  170 

oxide  of,  as  a  base  170 

protosulphate  of  .       .       .       .  .171 

compositions  of  171 

-  oxide  of,  as  an  acid  173 

mordants,  application  of  .  .  .  .  .174 
hyposulphite  of  180 

r  b 

Ungumming  silk  37 

Uric  acid  in  guano,  preparation  of     ...  186 

V  ' 

Violine  86 

to  dye  with      .       .       .       .       .       .       .  113 

% 

Wool  .       .      \       .       ...       ...  34 

Wool  with  aniline  purple,  violine,  roseine,  futscliine, 

to  dye  .       .       .       .       .       .       .       .  114 

with  chrysammic  acid,  dyeiug  .       .       .       .  126 

X 

Xylidine     .       .       ....       .       .       .       .  98 


DIRECTED  BY 


Prof.  H.  DUSSAUCE,  Chemist, 

Lately  from  the  Laboratories  of  the  French  Government,  viz.,  the  Mining, 
the  Botanical  Garden,  the  Imperial  Manufacture  of  the  Gobelins,  and, 
the  Conservatoire  Imperial  of  Arts  and  Manufactures,  etc. 


Advice  and  Consultations  on  Chemistry  as  applied  to  Arts  and  Manufac- 
tures, Agriculture,  Metallurgy,  Mining  Surveys,  Plans  of  Factories,  Draw- 
ings of  Apparatus,  Chemical  Manufactures,  Analysis  of  Ores,  Manures, 
Guanos,  Mineral  Waters,  Soils,  Plants,  Greases,  Oils,  Soaps,  Tallows,  and 
Commercial  Essays  in  General. 

Prof.  H.  Dussauce  will  undertake  experiments  on  any  industrial  subject, 
and  charge  nothing  except  for  the  actual  expenses  incurred. 

By  his  long  study  in  the  laboratories  of  the  French  government,  Prof.  H, 
Dussauce  has  in  his  possession  plans  and  drawings  of  Factories  and  Appa- 
ratus, and  would  send  them  to  any  person  desiring  their  use.  He  will  also 
give  advice,  information,  recipes,  etc.  etc.,  on  the  following  Arts: — 

Chemical  Products  —  Metallurgy — Galvanoplasty  —  Electro-Plating  and 
Gilding — Coal  and  Charcoal  —  Daguerreotype  Photography  —  Lighting  and 
Heating  by  Gas — White  and  Color  of  Zinc  and  Lead — Glass — Brick — Pottery 
— China — Limes — Plasters — Matches — Mineral,  Vegetable,  and  Animal  Oils 
— Saltpetre  and  Powder — Wines,  Beers,  Ciders,  and  Liquors  in  general — Dis- 
tillation— Starch — Sugar — Paper  —  Dyeing  and  Calico  Printing  —  Indigo — 
Inks — Leathers — Gelatine — India  Rubber  and  Gutta-Percha — Varnishes — 
Vegetable  Colors — Perfumery — Agriculture — Animal  Black — Natural  and  Ar- 
tificial Manures — Candles  and  Soap  of  every  description,  &c.  &c. 

For  consultation,  advice,  information,  recipes,  formulae,  drawings,  plans, 
analyses,  commercial  essays,  experiments,  &g., 

Address         Prof.  H.  DUSSAUCE,  Chemist, 

New  Lebanon,  N.  Y. 


REFER 

Dr.  H.  Townsend,  Albany. 
Dr.  A.  S.  Heath,  647  Broadway,  N.  Y. 
Dr.  D.  E.  Coutaret,  132  Thompson,  N.  Y. 
Prof.  H.  Cleveland,  Cincinnati,  Ohio. 
Ch.  Lassalle,  Ed.  of  the  Courrier  des  Etats 

Unis,  Walker  Street,  N.  Y. 
B.  Keis,  72  Beaver  Street. 
J.  C.  Hull  Sons,  32  Park  Row,  N.  Y. 


ENCES, 

H.  M.  Piatt,  21  Maiden  Lane,  N.  Y. 

B.  Darling,  Providence,  R.  I. 
Ph.  Tompert,  Louisville,  Ky. 

A.  Rapelye,  68  Cedar  Street,  N.  Y. 
A.  H.  Heath,  647  Broadway,  N.  Y. 

C.  Coyle,  Louisville,  Ky. 

F.  Emerich,  27  Maiden  Lane,  N.  Y. 
Thain  &  McKeone,  Philadelphia,  etc.  etc. 


PARTRIDGE  &  HARWAY, 


ALFRED  H.  PARTRIDGE. 


JAMES  L.  HARWAY. 


Office  IVo.  27  Cliff  Street,  New  York, 

Importers  and  Manufacturers  of  and  Dealers  in 

DYESTUPPS,   DYEWOODS,  ACIDS, 

Extract  Logwood^  cfco. 

Have  always  on  hand  from  our  Dyewood  Mills,  Extract  and  Chemical  Works, 
a  full  supply  of  the  following  articles,  and  offer  at  Wholesale  and  Retail, 


INDIGO. 

Bengal, 
Guatemala, 
Chemic, 
Indigo  Paste, 
Ext.  Indigo. 

DYE  STUFFS. 

Argols, 

Alum, 

Annotto, 

Bichromate  Potash, 

Blue  Vitriol, 

Cochineal, 

Cudbear, 

Cream  Tartar, 

Chlorate  Potash, 

Copper  Dust, 

Copperas, 

Cutch, 

Divi  Divi, 

French  Berries, 

Flavine, 

Lac  Dye, 

Litharge, 

Madder, 

Nitrate  Lead, 

Nut  Galls, 

Orchille, 

Persian  Berries, 

Prussiate  Potash, 

"  "  Red, 

Red  Orpiment, 
Safflower, 
Salts  Tartar, 
Sal  Ammoniac, 
Sugar  Lead,  white, 


Sugar  Lead,  brown, 
Soluble  Blue, 
Sumac, 

Terra  Japonica, 
Turkey  Berries, 
Turmeric, 
Tin, 

Verdigris, 
Valonia, 
Woad, 
Weld. 

DYEWOODS. 

Barbary  Root, 
Bar  Wood, 
Brazil  " 
Cam  " 
Fustic, 

Green  Ebony, 
Hyper  Nic, 
Hache  Wood, 
Log  " 
Nic 

Peach  " 
Red  " 
Sapan  " 
Red  Sanders, 
Maple  Bark, 
Quercitron  Bark. 

EXTRACTS. 

Ext.  Logwood, 
"  Fustic, 
"    Hyper  Nic, 
"  Quercitron, 
"  Safflower. 


ACIDS. 

Aqua  Fortis, 

"        "  Single, 
Aqua  Ammonia, 
Acetic  Acid, 
Crimson  Spirits, 
Citric  Acid, 
Dipping  " 
Iron  Liquor, 
Muriatic  Acid, 

"  "  Pure, 
Muriate  Tin, 

"  "  Strong, 
Nitric  Acid, 

it,  a  pure) 

Nitrate  Iron, 
Nitro-Mur.  Tin, 
Oxy-  " 
Sulph.  "  " 
Oxalic  Acid, 
Oil  Vitriol, 
Parting  Acid, 
Pyroligneous  Acid, 
Plumb  Spirits, 
Red  Liquor, 
Sapan  " 
Tin  Crystals, 
Tartaric  Acid, 

"  "  Ground 
Telegraphic  Acid. 

SUNDRIES. 

Alcohol, 
Acetate  Lime, 
Arsenic, 

Brimstone,  Roll, 


Bleaching  Salts, 
Borax, 
Bicarb.  Soda, 
Carb.  Ammonia, 
China  Clay, 
Fullers'  Earth, 
Flour  Sulphur, 
Glauber's  Salts, 
Gum  Arabic, 
"  British, 
"  Senegal, 
"  Shellac, 
"  Substitute, 
"  Tragacanth, 
Glue, 

Hydrometers, 

Irish  Moss, 

Manganese, 

Marble  Dust, 

Nitrate  Soda, 

Pot  Ashes, 

Pearl  " 

Rosin, 

Sal  Soda, 

Soda  Ash, 
"      "  Prepared, 

Sal  iEratus, 
"  Enixum, 
"  Acetosella, 

Sulph.  Zinc, 
"  Potash, 
"  Ammonia, 

Saltpetre, 

Teazles, 

Vat  Nets, 

Venetian  Red, 

Whiting. 


g^gr  Aniline  Colors  in  quantities  to  suit.  t*®H 


ANILINE  COLOKS; 


PRODUCTS  OF 

RENARD  ERERES,  AND  FRANC, 

I/YOISrS,  FRANCE, 

Secured  by  tetters  Patent  of  the  United  States  issued  31st  July, 
I860,  and  30th  July,  1861. 

These  Colors  are  known  as 

FEIiStSSQElg  ©IE  MB  {LB  El  IS  IBS®* 
YtOfcfiT  tMPfiftlAtt, 

AND 

BLEU   DE  LYON. 


The  undersigned,  SOLE  AGENTS  in  the  United  States,  offer 
for  sale  the  above  named  Colors,  and  will  furnish  upon  application, 
by  mail  or  otherwise,  full  directions  for  their  use. 


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New  York. 


GEORGE  M.  BRAGGIOTTI, 

MERCHANT  AND  AGENT 

i«t  l\t  "toppi*  feiranira*"  at  Smpra  snli  Cimstan- 

HAS  ALWAYS  ON  HAND 

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PRACTICAL  SCIENCE,  ARTS,  MANUFACTURES,  AGRICUL- 
TURE, AND  INDUSTRY  IN  GENERAL, 

Is  Edited  by  PROFESSOR  H.  DUSSAUCE, 

AND  IS  PUBLISHED  MONTHLY 

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JCr"  Any  of  the  following  Books  will  be  sent  by  mail,  free 
of  postage,  at  the  publication  price.  Catalogues  furnished 
on  application. 


American  Miller  and  Millwright's  Assistant: 

A  new  and  thoroughly  revised  Edition,  with  additional 
Engravings.  By  William  Cakter  Hughes.  In  one  vol- 
ume, 12  mo.,  $1.00 

Armengaud,  Amoroux,  and  Johnson, 

THE  PRACTICAL  DRAUGHTSMAN'S  BOOK  OF  INDUS- 
TRIAL DESIGN,  and  Machinist's  and  Engineer's  Drawing 
Companion  ;  forming  a  complete  course  of  Mechanical 
Engineering  and  Architectural  Drawing.  From  the  French 
of  M.  Armengaud  the  elder,  Prof,  of  Design  in  the  Con- 
servatoire of  Arts  and  Industry,  Paris,  and  MM.  Armen- 
gaud the  younger,  and  Amouroux,  Civil  Engineers.  Re- 
written and  arranged,  with  additional  matter  and  plates, 
selections  from  and  examples  of  the  most  useful  and 
generally  employed  mechanism  of  the  day.  By  William 
Johnson,  Assoc.  Inst.  C.  E.,  Editor  of  "The  Practical 
Mechanic's  Journal."  Illustrated  by  fifty  folio  steel 
plates  and  fifty  wood-cuts.    A  new  edition,  4to.,....$7.50 

Among  the  contents  are  : — Linear  Drawing,  Definitions  and  Problems, 
Plate  I.  Applications,  Designs  for  inlaid  Pavements,  Ceilings  and 
Balconies,  Plate  II.  Sweeps,  Sections  and  Mouldings,  Plate  III.  Ele 
mentary  Gothic  Forms  and  Rosettes,  Plate  IV.     Ovals,  Ellipses, 


PBACTICAL  AND  SCIENTIFIC  BOOKS, 


ParabolaB  and  Volutes,  Plate  V.  Rules  and  Practical  Data.  Study  of 
Projections,  Elementary  Principles,  Plate  VI.  Of  Prisms  and  other 
Solids,  Plate  VII.  Rules  and  Practical  Data.  On  Coloring  Sections,  with 
Applications — Conventional  Colors,  Composition  or  Mixture  of  Colors, 
Plate  X.  Continuation  of  the  Study  of  Projections — Use  of  sections— de- 
tails of  machinery,  Plate  XI.  Simple  applications—spindles,  shafts, 
couplings,  wooden  patterns,  Plate  XII.  Method  of  constructing  a 
wooden  model  or  pattern  of  a  coupling,  Elementary  applications — 
rails  and  chairs  for  railways,  Plate  XIII.  Rules  and  Practical  Data-~ 
Strength  of  material,  Resistance  to  compression  or  crushing  force, 
Tensional  Resistance,  Resistance  to  flexure,  Resistance  to  torsion, 
Friction  of  surfaces  in  contact. 

The  Intersection  and  Development  of  Surfaces,  with  Ap- 
plications.— The  Intersection  of  Cylinders  and  Cones,  Plate  XIV.  The 
Delineation  and  Development  of  Helices,  Screws  &nd  Serpentines,  Plate 

XV.  Application  of  the  helix — the  construction  of  a  staircase,  Plate 

XVI.  The  Intersection  of  surfaces — applications  to  stop-cocks,  Plate 

XVII.  Rules  and  Practical  Data — Steam,  Unity  of  heat,  Heating  surface, 
Calculation  of  the  dimensions  of  boilers,  Dimensions  of  firegrates, 
Chimneys,  Safety-valves. 

The  Study  and  Construction  of  Toothed  Gear.— Involute,  cy- 
cloid, and  epicycloid,  Plates  XVIII.  and  XIX.    Involute,  Fig.  1,  Plate 

XVIII.  Cycloid,  Fig.  2,  Plate  XVIII.  External  epicycloid,  described 
by  a  circle  rolling  about  &  fixed  circle  inside  it,  Fig.  3,  Plate  XIX. 
Internal  epicycloid,  Fig.  2,  Plate  XIX.  Delineation  of  a  rack  and 
pinion  in  gear,  Fig.  4,  Plate  XVIII.  Gearing  of  a  worm  with  a  worm- 
wheel,  Figs.  5  and  6,  Plate  XVIII.    Cylindrical  or  Spur  Gearing,  Plate 

XIX.  Practical  delineation  of  a  couple  of  Spur-wheels,  Plate  XX. 
The  Delineation  and  Construction  of  Wooden  Patterns  for  Toothed  Wheels. 
Plate  XXI.  Rules  and  Practical  Data — Toothed  gearing,  Angular  ana 
circumferential  velocity  of  wheels,  Dimensions  of  gearing,  Thickness 
of  the  teeth,  Pitch  of  the  teeth,  Dimensions  of  the  web,  Number  and 
dimensions  of  the  arms,  wooden  patterns. 

Continuation  of  the  Study  of  Toothed  Gear.— Design  for  a 
pair  of  bevel-wheels  in  gear,  Plate  XXII.  Construction  of  wooden 
patterns  for  a  pair  of  bevel-wheels,  Plate  XXIII.  Involute  and 
Helical  Teeth,  Plate  XXIV.  Contrivances  for  obtaining  Differential 
Movements — The  delineation  of  eccentrics  and  cams,  Plate  XXV.  Rules 
and  Practical  Data— Mechanical  work  of  effect,  The  simple  machines, 
Centre  of  gravity,  On  estimating  the  power  of  prime  movers,  Calcu- 
lation for  the  brake,  The  fall  of  bodies,  Momentum,  Central  forces. 

Elementary  Principles  of  Shadows. — Shadows  of  Prisms,  Pyra- 
mids and  Cylinders,  Plate  XXVI.  Principles  of  Shading,  Plate  XXVII. 
Continuation  of  the  Study  of  Shadows,  Plate  XXVIII.  Tuscan  Order, 
Plate  XXIX.  Rules  and  Practical  Data — Pumps,  Hydrostatic  principles, 
Forcing  pumps,  Lifting  and  forcing  pumps,  The  Hydrostatic  press, 
Hydrostatical  calculations  and  data — discharge  of  water  through  dif- 
ferent orifices,  Gaging  of  a  water-course  of  uniform  section  and  fall, 
Velocity  of  the  bottom  of  water-courses,  Calculation  of  the  discharge 
of  water  through  rectangular  orifices  of  narrow  edges,  Calculation  of 
the  discharge  of  water  through  overshot  outlets,  To  determine  the 
width  of  an  overshot  outlet,  To  determine  the  depth  of  the  outlet, 
Outlet  with  a  spout  or  duct. 

Application  of  Shadows  to  Toothed  Gear,  Plate  XXX.  Ap- 
plication of  Shadows  to  Screws,  Plate  XXXI.  Application  of  Shadows  to 
a  Boiler  and  its  Furnace,  Plate  XXXII.  Shading  in  Black — Shading  in 
Colors,  Plate  XXXIII. 

The  Cutting  and  Shaping  of  Masonry,  Plate  XXXIV.  Rules 
and  Practical  Data — Hydraulic  motors,  Undershot  water  wheels,  with 
plane  floats  and  a  circular  channel,  Width,  Diameter,  Velocity,  Num- 
ber and  capacity  of  the  buckets,  Useful  effect  of  the  water  wheel. 
Overshot  water  wheels,  Water  wheels  with  radial  floats,  Water  wheel 
with  curved  buckets,  Turbines.  Remarks  on  Machine  Tools, 
2 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


The  Study  of  Machinery  and  Sketching.— Various  applications 
and  combinations  :  The  Sketching  of  Machinery,  Plates  XXXV.  and 
XXXVI.  Drilling  Machine;  Motive  Machines;  Water  wheels,  Con- 
struction and  setting  up  of  water  wheels,  Delineation  of  water  wheels, 
Design  for  a  water  wheel,  Sketch  of  a  water  wheel ;  Overshot  Water 
Wheels.  Water  Pumps,  Plate  XXXVII.  Steam  Motors;  High-pressure 
expansive  steam  engine,  Plates  XXXVIII.,  XXXIX.  and  XL.  Details 
of  Construction  ;  Movements  of  the  Distribution  and  Expansion  Valves  ; 
Rules  and  Practical  Data — Steam  engines  :  Low-pressure  condensing 
engines  without  expansion  valve,  Diameter  of  piston,  Velocities. 
Steam  pipes  and  passages,  Air-pump  and  condenser,  Cold-water  ana 
feed-pumps,  High-pressure  expansive  engines,  Medium  pressure  con- 
densing and  expansive  steam  engine,  Conical  pendulum  or  centrifugal 
governor. 

Oblique  Projections. — Application  of  rules  to  the  delineation  of 
an  oscillating  cylinder,  Plate  XLI. 

Parallel  Perspective. — Principles  and  applications,  Plate  XLII. 

True  Perspective. — Elementary  principles,  Plate  XLIII.  Appli- 
cations— flour  mill  driven  by  belts,  Plates  XLIV.  and  XLV.  Descrip- 
tion of  the  mill,  Representation  of  the  mill  in  perspective,  Notes  of 
recent  improvements  in  flour  mills,  Schiele's  mill,  Mullin's  "  ring  mill- 
stone," Barnett's  millstone,  Hastie's  arrangement  for  driving  mills, 
Currie's  improvements  in  millstones  ;  Rules  and  Practical  Data — Work 
performed  by  various  machines.  Flour  mills,  Saw  mills,  Veneer-sawing 
•machines,  Circular  saws. 

Examples  of  Finished  Drawings  of  Machinery. — Plate  A, 
Balance  water-meter ;  Plate  B,  Engineer's  shaping  machine ;  Plate 
C  D  E,  Express  locomotive  engine  ;  Plate  F.,  Wood  planing  machine  ; 
Plate  G,  Washing  machine  for  piece  goods  ;  Plate  H,  power  loom  ; 
Plate  I,  Duplex  steam  boiler ;  Plate  J,  Direct-acting  marine  engines. 

Drawing  Instruments. 

Barnard  (Henry),   National  Education  in  Eu- 
rope: 

Being  an  Account  of  the  Organization,  Administration, 
Instruction,  and  Statistics  of  Public  Schools  of  differ- 
ent grades  in  the  principal  States.  890  pages,  8vo., 
cloth,  $3.00 

Barnard  (Henry),    School  Architecture, 

New  Edition,  300  cuts,  cloth,  $2.00 

Beans,  A  Treatise  on  Railroad  Curves  and  the 
Location  of  Railroads. 

By  E.  W.  Beans,  C.  E.    12mo.    (In  press.) 

Bishop,   A  History  of  American  Manufactures, 

From  1608  to  1860  ;  exhibiting  the  Origin  and  Growth 
of  the  Principal  Mechanic  Arts  and  Manufactures,  from 
the  Earliest  Colonial  Period  to  the  Present  Time  ;  with  a 


PKACTICAIi  AND  SCIENTIFIC  BOOKS, 


Notice  of  the  Important  Inventions,  Tariffs,  and  the  Re- 
sults of  each  Decennial  Census.  By  J.  Leander  Bishop, 
M.  D,  :  to  which  is  added  Notes  on  the  Principal  Manu- 
facturing Centres  and  Remarkable  Manufactories.  By 
Edward  Young  and  Edwin  T.  Freedley.  In  two  vols., 
8vo.    Vol.  1  now  ready.    Price,  $3.00 

Bookbinding  s  A  Manual  of  the  Art  of  Book* 

binding, 

Containing  full  instructions  in  the  different  branches  of 
Forwarding,  Gilding  and  Finishing.  Also,  the  Art  of 
Marbling  Book-edges  and  Paper.  By  James  B.  Nicholson. 
Illustrated     12mo.,  cloth,  $1.75 

CONTENTS.— Sketch  of  the  Progress  of  Bookbinding,.  Sheet- 
work,  Forwarding  the  Edges,  Marbling,  Gilding  the  Edges,  Covering, 
Half  Binding,  Blank  Binding,  Boarding,  Cloth-work,  Ornamental  Art, 
Finishing,  Taste  and  Design,  Styles,  Gilding,  Illuminated  Binding, 
Blind  Tooling,  Antique,  Coloring,  Marbling,  Uniform  Colors,  Gold 
Marbling,  Landscapes,  etc.,  Inlaid  Ornaments,  Harmony  of  Colors, 
Pasting  Down,  etc.,  Stamp  or  Press-work,  Restoring  the  Bindings  of 
Old  Books,  Supplying  imperfections  in  Old  Books,  Hints  to  Book  Col- 
lectors, Technical  Lessons. 

Booth  and  Morfit,    The  Encyclopedia  of 
Chemistry,  Practical  and  Theoretical : 

Embracing  its  application  to  the  Arts,  Metallurgy,  Mine- 
ralogy, Geology,  Medicine,  and  Pharmacy,  By  James  C. 
Booth,  Melter  and  Refiner  in  the  United  States  Mint  ; 
Professor  of  Applied  Chemistry  in  the  Franklin  Institute, 
etc.;  assisted  by  Campbell  Morfit,  author  of  "  Chemical 
Manipulations,"  etc.  7th  Edition.  Complete  in  one 
volume,  royal  octavo,  978  pages,  with  numerous  wood 
cuts  and  other  illustrations,  $5.00 

From  the  very  large  number  of  articles  in  this  volume,  it  is  entirely 
impossible  to  give  a  list  of  the  Contents,  but  attention  may  be  called 
to  some  among  the  more  elaborate,  such  as  Affinity,  Alcoholometry, 
Ammonium,  Analysis,  Antimony,  Arsenic,  Blowpipes,  Cyanogen,  Dis- 
tillation, Electricity,  Ethyl,  Fermentation,  Iron,  Lead  and  Water. 

Brewer;  (The  Complete  Practical) 

Or  Plain,  Concise,  and  Accurate  Instructions  in  the  Art 
of  Brewing  Beer,  Ale,  Porter,  etc.,  etc.,  and  the  Process 
of  Making  all  the  Small  Beers.    By  M.  Lafayette  Bykn, 

M.  D.    With  Illustrations.    12mo  $1.00 

"  Many  an  old  brewer  will  find  in  this  book  valuable  hints  and  sug- 


PUBLISHED  BY  HENRY  CAREY  BAIHD. 


gestions  worthy  of  consideration,  and  the  novice  can  post  himself  up 
in  his  trade  in  all  its  parts,"— Artisan. 

Builder's  Pocket  Companion: 

Containing  the  Elements  of  Building,  Surveying,  and 
Architecture  ;  with  Practical  Rules  and  Instructions  con- 
nected with  the  subject.  By  A.  C.  Smeaton,  Civil  Engi- 
neer, etc.    In  one  volume,  12mo.,  $1.00 

CONTENTS-The  Builder,  Carpenter,  Joiner,  Mason,  Plasterer, 
Plumber,  Painter,  Smith,  Practical  Geometry,  Surveyor,  Cohesive 
Strength  of  Bodies,  Architect. 

"  It  gives,  in  a  small  space,  the  most  thorough  directions  to  the 
builder,  from  the  laying  of  a  brick,  or  the  felling  of  a  tree,  up  to  the 
most  elaborate  production  of  ornamental  architecture.  It  is  scientific, 
without  being  obscure  and  unintelligible  ;  and  every  house-carpenter, 
master,  journeyman,  or  apprentice,  should  have  a  copy  at  hand 
always."—  Evening  Bulletin. 

Byrne,   The  Handbook  for  the  Artisan,  Me- 
chanic, and  Engineer, 

Containing  Instructions  in  Grinding  and  Sharpening  of 
Cutting  Tools,  Figuration  of  Materials  by  Abrasion,  Lapi- 
dary Work,  Gem  and  Glass  Engraving,  Varnishing  and 
Lackering,  Abrasive  Processes,  etc.,  etc.  By  Oliver 
Byrne.  Illustrated  with  11  large  plates  and  185  cuts. 
8vo.,  cloth,  $5.00 

CONTENTS— Grinding  .Cutting  Tools  on  the  Ordinary  Grind- 
stone ;  Sharpening  Cutting  Tools  on  the  Oilstone  ;  Setting  Razors ; 
Sharpening  Cutting  Tools  with  Artificial  Grinders  ;  Production  of  Plane 
Surfaces  by  Abrasion ;  Production  of  Cylindrical  Surfaces  by  Abra- 
sion ;  Production  of  Conical  Surfaces  by  Abrasion  ;  Production  of 
Spherical  Surfaces  by  Abrasion;  Glass  Cutting;  Lapidary  Work; 
Setting,  Cutting,  and  Polishing  Flat  and  Rounded  Works;  Cutting 
Faucets  ;  Lapidary  Apparatus  for  Amateurs  ;  Gem  and  Glass  Engrav- 
ing ;  Seal  and  Gem  Engraving ;  Cameo  Cutting ;  Glass  Engraving, 
Varnishing,  and  Lackering ;  General  Remarks  upon  Abrasive  Pro- 
cesses ;  Dictionary  of  Apparatus  ;  Materials  and  Processes  for  Grinding 
and  Polishing  commonly  employed  in  the  Mechanical  and  Useful  Arts. 

Byrne.   The  Practical  Metal- worker's  Assist- 
ant, 

For  Tin-plate  Workers,  Braziers,  Coppersmiths,  Zinc- 
plate  Ornrmenters  and  Workers,  Wire  Workers,  White- 
smiths, Blacksmiths,  Bell  Hangers,  Jewellers,  Silver  and 
Gold  Smiths,  Electrotypers,  and  all  other  Workers  in 
Alloys  and  Metals.  Edited  by  Oliver  Byrne.  Complete 
in  one  volume,  octavo,  $7.50 

It  treats  of  Casting,  Founding,  and  Forging;  of  Tongs  and  other 
Tools ;  Degrees  of  Heat  and  Management  of  Fires ;  Welding  of 

5 


PBACTICAIj  and  scientific  books, 


Heading  and  Swage  Tools  ;  of  Punches  and  Anvils  ;  of  Hardening  and 
Tempering;  of  Malleable  Iron  Castings,  Case  Hardening,  Wrought 
and  Cast  Iron;  the  Management  and  Manipulation  of  Metals  and 
Alloys,  Melting  and  Mixing  ;  the  Management  of  Furnaces,  Casting 
and  Founding  with  Metallic  Moulds,  Joining  and  Working  Sheet  Metal ; 
Peculiarities  of  the  different  Tools  employed  ;  Processes  dependent  on 
the  ductility  of  Metals  ;  Wire  Drawing,  Drawing  Metal  Tubes,  Solder- 
ing ;  The  use  of  the  Blowpipe,  and  every  other  known  Metal  Worker's 
Tool. 

Byrne,   The  Practical  Model  Calculator, 

For  the  Engineer,  Machinist,  Manufacturer  of  Engine 
Work,  Naval  Architect,  Miner,  and  Millwright.  By 
Oliver  Byrne,  Compiler  and  Editor  of  the  Dictionary  of 
Machines,  Mechanics,  Engine  Work  and  Engineering,  and 
Author  of  various  Mathematical  and  Mechanical  Works. 
Illustrated  by  numerous  engravings.  Complete  in  one 
large  volume,  octavo,  of  nearly  six  hundred  pages,. .$3. 50 

The  principal  objects  of  this  work  are  :  to  establish  model  calcula- 
tions to  guide  practical  men  and  students  ;  to  illustrate  every  practical 
rule  and  principle  by  numerical  calculations,  systematically  arranged  ; 
to  give  information  and  data  indispensable  to  those  for  whom  it  is  in- 
tended, thus  surpassing  in  value  any  other  book  of  its  character ;  to 
economize  the  labor  of  the  practical  man,  and  to  render  his  every-day 
calculations  easy  and  comprehensive.  It  will  be  found  to  be  one  of 
the  most  complete  and  valuable  practical  books  ever  published. 

Cabinetmaker's  and  Upholsterer's  Companion, 

Comprising  the  Rudiments  and  Principles  of  Cabinet- 
making  and  Upholstery,  with  Familiar  Instructions,  il- 
lustrated by  Examples  for  attaining  a  proficiency  in 'the 
Art  of  Drawing,  as  applicable  to  Cabinet  Work  ;  the 
processes  of  Veneering,  Inlaying,  and  Buhl  Work  ;  the 
Art  of  Dyeing  and  Staining  Wood,  Bone,  Tortoise  Shell, 
etc.  Directions  for  Lackering,  Japanning,  and  Varnish- 
ing ;  to  make  French  Polish  ;  to  prepare  the  best  Glues, 
Cements,  and  Compositions,  and  a  number  of  Receipts 
particularly  useful  for  Workmen  generally.  By  J.  Stokes. 
In  one  volume,  12mo.    With  Illustrations,   75 

"  A  large  amount  of  practical  information,  of  great  service  to  all 
concerned  in  those  branches  of  business." — Ohio  State  Journal. 

Campion,  A  Practical  Treatise  on  Mechanical 
Engineering; 

Comprising  Metallurgy,  Moulding,  Casting,  Forging  Tools, 
Workshop  Machinery,  Mechanical  Manipulation,  Manu- 
facture of  Steam  Engine,  etc.,  etc.  Illustrated  with  28 
plates  of  Boilers,  Steam  Engines,  Workshop  Machinery, 
6 


PUBLISHED  BY  HENEY  CAREY  BAIRD. 


etc.,  and  91  Wood  Engravings  ;  with  an  Appendix  on  the 
Analysis  of  Iron  and  Iron  Ores.  By  Francis  Campion, 
C.  E.,  President  of  the  Civil  and  Mechanical  Engineers' 
Society,  etc.    (In  press.) 

Celnart.   The  Perfumer. 

From  the  French  of  Madame  Celnart  ;  with  additions  by 
Professor  H.  Dussauce.    8vo.    (/» press.) 

Colburn.   The  Locomotive  Engine ; 

Including  a  Description  of  its  Structure,  Rules  for  Esti- 
mating its  Capabilities,  and  Practical  Observations  on  its 
Construction  and  Management.  By  Zerah  Colburn.  Il- 
lustrated.   A  new  edition.    12mo,   75 

"  It  is  the  most  practical  and  generally  useful  work  on  the  Steam 
Engine  that  we  have  seen." — Boston  Trawler." 

Dagnerreotypist  and  Photographer's  Companion, 

12mo.,  cloth,  $1.00 

Distiller  (The  Complete  Practical), 

By  M.  Lafayette  Byrn,  M.D.    With  Illustrations.  12mo. 

$1.00 

M  So  simplified,  that  it  is  adapted  not  only  to  the  use  of  extensive 
Distillers,  but  for  every  farmer,  or  others  who  may  want  to  engage  in 
Distilling." — Banner  of  the  Union. 

Dussauce,   Practical  Treatise 

On  the  Fabrication  of  Matches,  Gun  Cotton,  and  Fulmi- 
nating Powders.    By  Prof.  H.  Dussauce.    (In  press.) 

CONTENTS  —  Phosphorus.  —History  of  Phosphorus;  Physical 
Properties  ;  Chemical  Properties ;  Natural  State ;  Preparation  of 
White  Phosphorus  ;  Amorphous  Phosphorus,  and  Benoxide  of  Lead. 
Matches. — Preparation  of  Wooden  Matches ;  Matches  inflammable  by 
rubbing,  without  noise  ;  Common  Lucifer  Matches  :  Matches  without 
Phosphorus ;  Candle  Matches  ;  Matches  with  Amorphous  Phospho- 
rus ;  Matches  and  Rubbers  without  Phosphorus.  Gun  Cotton. — Proper- 
ties ;  Preparation  ;  Paper  Powder  ;  use  of  Cotton  and  Paper  Powders 
for  Fulminating  Primers,  etc.;  Preparation  of  Fulminating  Primers, 
etc.,  etc. 

Dussauce.    Chemical  -Receipt  Book : 

A  General  Formulary  for  the  Fabrication  of  Leading 
Chemicals,  and  their  Application  to  the  Arts,  Manufac- 
tures, Metallurgy,  and  Agricu  ture.  By  Prof.  H.  Dus- 
sauce.   (/«  press.) 


PEACTICAIi  AND  SCIENTIFIC  BOOKS. 


DYEING,  CALICO  PEINTING,  COLOES,  COTTON  SPIN- 
NING, AND  WOOLEN  MANUFACTURE. 

Baird.   The  American  Cotton  Spinner,  and 
Manager's  and  Carder's  Guide: 

A  Practical  Treatise  on  Cotton  Spinning  ;  giving  the  Di- 
mensions and  Speed  of  Machinery,  Draught  and  Twist 
Calculations,  etc.;  with  Notices  of  recent  Improvements  : 
together  with  Rules  and  Examples  for  making  changes 
in  the  sizes  and  numbers  of  Roving  and  Yarn.  Com- 
piled from  the  papers  of  the  late  Robert  H.  Baird. 
12mo  $1.25 

Capron  De  Dole,   Dnssauce,   Blues  and  Car- 
mines of  Indigo: 

A  Practical  Treatise  on  the  Fabrication  of  every  Commer- 
cial Product  derived  from  Indigo.  By  Felicien  Capron 
de  Dole.  Translated,  with  important  additions,  by  Pro- 
fessor H.  Dussauce.    12mo  $2.50 

Chemistry  Applied  to  Dyeing, 

By  James  Napier,  F.  C.  S.    Illustrated.   12mo  $2.00 

CONTENTS—  General  Properties  of  Matter.— Heat,  Light,  Ele- 
ments of  Matter,  Chemical  Affinity.  Non-Metallic  Substances. — Oxygen, 
Hydrogen,  Nitrogen,  Chlorine,  Sulphur,  Selenium,  Phosphorus,  Iodine, 
Bromine,  Fluorine,  Silicum,  Boron,  Carbon.  Metallic  Substances. — 
General  Properties  of  Metals,  Potassium,  Sodium,  Lithium,  Soap, 
Barium,  Strontium,  Calcium,  Magnesium,  Alminum,  Manganese,  Iron, 
Cobalt,  Nickel,  Zinc,  Cadmium,  Copper,  Lead,  Bismuth,  Tin,  Titanium, 
Chromium,  Vanadium,  Tungstenum  or  Wolfram,  Molybdenum,  Tella- 
rium,  Arsenic,  Antimony,  Uranium,  Cerium,  Mercury,  Silver,  Gold, 
Platinum,  Palladium,  Iridium,  Osmium,  Rhodium,  Lanthanium.  Mor- 
dants.— Red  Spirits,  Barwood  Spirits,  Plumb  Spirits?  Yellow  Spirits, 
Nitrate  of  Iron,  Acetate  of  Alumina>  Black  Iron  Liquor,  Iron  and  Tin 
for  Royal  Blues,  Acetate  of  Copper.  Vegetable  Matters  used  in  Dyeing. — 
Galls,  Sumach,  Catechu,  Indigo,  Logwood,  Brazil-woods,  Sandal-wood, 
Barwood,  Camwood,  Fustic,  Young  Fustic,  Bark  or  Quercitron,  Fla- 
vine,  Weld  or  Wold,  Turmeric,  Persian  Berries,  Safflower,  Madder, 
Munjeet,  Annota,  Alkanet  Root,  Archil.  Proposed  New  Vegetable 
Dyes. — Sooranjee,  Carajuru,  Wongshy,  Aloes,  Pittacal,  Barbary  Root. 
Animal  Matters  used  in  Dyeing. — Cochineal,  Lake  or  Lac,  Kerms. 

This  vflill  be  found  one  of  the  most  valuable  books  on  the  subject  of 
dyeing,  ever  published  in  this  country. 

Dussauce.   Treatise  on  the  Coloring  Matters 
Derived  from  Coal  Tar; 

Their  Practical  Application  in  Dyeing  Cotton,  Wool,  and 

8 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


Silk  ;  the  Principles  of  the  Art  of  Dyeing  and  of  the  Dis- 
tillation of  Coal  Tar;  with  a  Description  of  the  most  Im- 
portant New  Dyes  now  in  use.  By  Professor  H.  Dus- 
sauce,  Chemist.    12mo  $2.50 

CONTENTS— Historical  Notice  of  the  Art  of  Dyeing— Chemical 
Principles  of  the  Art  of  Dyeing— Preliminary  Preparation  of  Stuffs — 
Mordants — Dyeing — On  the  Coloring  Matters  produced  by  Coal  Tar — 
Distillation  of  Coal  Tar — History  of  Aniline— Properties  of  Aniline — 
Preparation  of  Aniline  directly  from  Coal  Tar— Artificial  Preparation 
of  Aniline — Preparation  of  Benzole — Properties  of  Benzole — Prepara- 
tion of  Nitro-Benzole — Transformation  of  Nitro-Benzole  into  Aniline, 
by  means  of  Sulphide  of  Ammonium  ;  by  Nascent  Hydrogen  ;  by  Ace- 
tate of  Iron  ;  and  by  Arsenite  of  Potash — Properties  of  the  Bi-Nitro- 
Benzole— Aniline  Purple — Violine  —  Roseine  —  Emeraldine  —  Bleu  de 
Paris — Futschine,  or  Magenta — Coloring  Matters  obtained  by  other 
bases  from  Coal  Tar — Nitroso-Phenyline — Di  Nitro-Aniline — Nitro- 
Phenyline— Picric  Acid— Rosolic  Acid— Quinoline — Napthaline  Colors 
— Chloroxynaphthalic  and  Perchloroxynapthalic  Acids — Carminaph- 
tha — Ninaphthalamine — Nitrosonaphthaline — Naphthamein — Tar  Red 
— Azuline — Application  of  Coal  Tar  Colors  to  the  Art  of  Dyeing  and 
Calico  Printing — Action  of  Light  on  Coloring  Matters  from  Coal  Tar 
— Latest  Improvements  in  the  Art  of  Dyeing — Chrysammic  Acid — Mo- 
lybdic  and  Picric  Acids — Extract  of  Madder — Theory  of  the  Fixation 
of  Coloring  Matters  in  Dyeing  and  Printing — Principles  of  the  Action 
of  the  most  important  Mordants — Aluminous  Mordants — Ferruginous 
Mordants — Stanniferous  Mordants — Artificial  Alizarin — Metallic  Hy- 
posulphites as  Mordants — Dyer's  Soap — Preparation  of  Indigo  for  Dye- 
ing and  Printing — Relative  value  of  Indigo — Chinese  Green  Murexide. 

Dyer  and  Color-maker's  Companion: 

Containing  upwards  of  two  hundred  Receipts  for  making 
Colors,  on  the  most  approved  principles,  for  all  the 
various  styles  and  fabrics  now  in  existence  ;  with  the 
Scouring  Process,  and  plain  Directions  for  Preparing, 
Washing-off,  and  Finishing  the  Goods.  Second  edition. 
In  one  volume,  12mo   75 

French  Dyer,  (The) : 

Comprising  the  Art  of  Dyeing  in  Woolen,  Silk,  Cotton, 
etc.,  etc.  By  M.  M.  Riffault,  Vernaud,  De  Fontenelle, 
Thillaye,  and  Mallepeyre.    {In  press.) 

Love,  The  Art  of  Dyeing,  Cleaning,  Scouring, 
and  Finishing, 

On  the  Most  Approved  English  and  French  Methods  ; 
being  Practical  Instructions  in  Dyeing  Silks,  Woolens 
and  Cottons,  Feathers,  Chips,  Straw,  etc.,  Scouring  and 
Cleaning  Bed  and  Window  Curtains,  Carpets,  Rugs,  etc., 
French  and  English  Cleaning,  any  Color  or  Fabric  of 
Silk,  Satin,  or  Damask.  By  Thomas  Love,  a  working 
Dyer  and  Scourer.    In  one  volume,  12mo  $3.00 


PBACTICAL  AND  SCIENTIFIC  BOOKS, 


O'Neill,   Chemistry  of  Calico  Printing,  Dye- 
ing, and  Bleaching ; 

Including  Silken,  Woolen,  and  Mixed  Goods  ;  Practical 
and  Theoretical.    By  Charles  O'Neill.    (In  press.) 

O'M'I.   A  Dictionary  of  Calico  Printing  and 

Dyeing. 

By  Charles  O'Neill.    (In  press.) 

Scott,  The  Practical  Cotton«spinner  and  Man- 
ufacturer ; 

Or,  The  Manager  and  Overlooker's  Companion.  This 
work  contains  a  Comprehensive  System  of  Calculations 
for  Mill  Gearing  and  Machinery,  from  the  first  Moving 
Power,  through  the  different  processes  of  Carding,  Draw- 
ing, Slabbing,  Roving,  Spinning,  and  Weaving,  adapted 
to  American  Machinery,  Practice  and  Usages.  Compen- 
dious Tables  of  Yarns  and  Reeds  are  added.  Illustrated 
by  large  Working-Drawings  of  the  most  approved  Ameri- 
can Cotton  Machinery.  Complete  in  one  volume,  oc- 
tavo $3.50 

This  edition  of  Scott's  Cotton-Spinner,  by  Oliver  Byrne,  is  designed 
for  the  American  Operative.  It  will  be  found  intensely  practical,  and 
will  be  of  the  greatest  possible  value  to  the  Manager,  Overseer,  and 
Workman. 

Sellers.   The  Color-mixer, 

By  John  Sellers,  an  Experienced  Practical  Workman. 
To  which  is  added  a  Catechism  of  Chemistry.  In  one 
volume,  12mo.    (In  press.) 

Smith,   The  Dyer's  Instructor; 

Comprising  Practical  Instructions  in  the  Art  of  Dyeing 
Silk,  Cotton,  Wool  and  Worsted,  and  Woolen  Goods,  as 
Single  and  Two-colored  Damasks,  Moreens,  Camlets, 
Lastings,  Shot  Cobourgs,  Silk  Striped  Orleans,  Plain  Or- 
leans, from  White  and  Colored  Warps,  Merinos,  Woolens, 
Yarns,  etc.;  containing  nearly  eight  hundred  Receipts. 
To  which  is  added  a  Treatise  on  the  Art  of  Padding,  and 
the  Printing  of  Silk  Warps,  Skeins  and  Handkerchiefs, 
and  the  various  Mordants  and  Colors  for  the  different 
10 


PUBLISHED  BY  HENEY  CAREY  BAIRD. 


styles  of  such  work.  By  David  Smith,  Pattern  Dyer. 
A  new  edition,  in  one  volume,  12mo  $3.00 

CONTENTS— Wool  Dyeing,  60  receipts— Cotton  Dyeing,  68  re- 
ceipts—Silk Dyeing,  60  receipts — Woolen  Yarn  Dyeing,  59  receipts — 
Worsted  Yarn  Dyeing,  51  receipts — Woolen  Dyeing,  62  receipts — Da- 
mask Dyeing,  40  receipts — Moreen  Dyeing,  38  receipts — Two-Colored 
Damask  Dyeing,  21  receipts — Camlet  Dyeing,  23  receipts — Lasting  Dye- 
ing, 23  receipts — Shot  Cobourg  Dyeing,  18  receipts — Silk  Striped  Or- 
leans, from  Black,  White,  and  Colored  Warps,  23  receipts — Colored 
Orleans,  from  Black  Warps,  15  receipts — Colored  Orleans  and  Co- 
bourgs,  from  White  Warps,  27  receipts — Colored  Merinos,  41  receipts 
— Woolen  Shawl  Dyeing,  15  receipts — Padding,  42  receipts — Silk  Warp, 
Skein,  and  Handkerchief  Printing,  62  receipts — Nature  and  Use  of  Dye- 
waaes,  including  Alum,  Annotta,  Archil,  Ammonia,  Argol,  Super 
Argol,  Camwood,  Catechu,  Cochineal,  Chrome,  or  Bichromate  of  Pot- 
ash, Cudbear,  Chemic,  or  Sulphate  of  Indigo,  French  Berry,  or  Persian 
Berry,  Fustic  or  Young  Fustic,  Galls,  Indigo,  Kermes  or  Lac  Dye, 
Logwood,  Madder,  Nitric  Acid  or  Aqua  Fortis,  Nitrates,  Oxalic  Tin, 
Peachwood,  Prussiate  of  Potash,  Quercitron  Bark,  Saffiower,  Saun- 
ders or  Red  Sandal,  Sapan  Wood,  Sumach,  Turmeric,  Examination  of 
Water  by  Tests,  etc.,  etc. 

Toustain.  A  Practical  Treatise  on  the  Woolen 
Manufacture. 

From  the  French  of  M.  Toustain.    (In  press.) 

CJlrich.   Dussauce,   A  Complete  Treatise 

On  the  Art  of  Dyeing  Cotton  and  Wool,  as  practised  in 
Paris,  Rouen,  Mulhouse  and  Germany.  From  the  French 
of  M.  Louis  Ulrich,  a  Practical  Dyer  in  the  principal 
Manufactories  of  Paris,  Rouen,  Mulhouse,  etc.,  etc.  ;  to 
which  are  added  the  most  important  Receipts  for  Dyeing 
Wool,  as  practised  in  the  Manufacture  Imperiale  des 
Gobelins,  Paris.  By  Professor  H.  Dussauce.  12mo,.$3.00 
CONTENTS.— 

Rouen  Dyes,  106  Receipts. 

Alsace      "     235  " 

German    "     109  " 

Mulhouse  "      72  " 

Parisian    "      66  " 

Gobelins   "     100  « 
In  all  nearly  700  Receipts. 


Easton,   A  Practical  Treatise  on  Street  or 
Horse-power  Railways; 

Their  Location,  Construction  and  Management ;  with 
general  Plans  and  Rules  for  their  Organization  and  Ope- 
ration ;  together  with  Examinations  as  to  their  Compara- 

11 


PKACTICAL  AND  SCIENTIFIC  BOOKS, 


tive  Advantages  over  the  Omnibus  System,  and  Inquiries 
as  to  their  Value  for  Investment ;  including  Copies  of 
Municipal  Ordinances  relating  thereto.  By  Alexander 
Easton,  C.  E.  Illustrated  by  twenty-three  plates,  8vo., 
cloth  $2.00 


Examinations  of  Drugs,  Medicines,  Chemicals, 
etc, 

As  to  their  Purity  and  Adulterations.  By  C.  H.  Peirce, 
M.  D.    12mo.,  cloth  $2.00 

Fisher's  Photogenic  Manipulation, 

16mo.,  cloth   62 

Gas  and  Ventilation; 

A  Practical  Treatise  on  Gas  and  Ventilation.  By  E.  E. 
Perkins.    12mo.,  cloth   75 

Gilhart,   A  Practical  Treatise  on  Banking, 

By  James  William  Gilbart,  F.  R.  S.  A  new  enlarged  and 
improved  edition.  Edited  by  J.  Smith  Homans,  editor 
of  "  Banker's  Magazine. "  To  which  is  added  "  Money,'* 
by  H.  C.  Carey.    8vo  $3.00 

Gregory's  Mathematics  for  Practical  Men; 

Adapted  to  the  Pursuits  of  Surveyors,  Architects,  Me- 
chanics and  Civil  Engineers.    8vo.,  plates,  cloth. ..$1.50 

Hardwich,   A  Manual  of  Photographic  Chem- 
istry ; 

Including  the  practice  of  the  Collodion  Process.  By  J. 
F.  Hardwich.    (In  press.) 

Hav.   The  Interior  Decorator; 

The  Laws  of  Harmonious  Coloring  adapted  to  Interior 
Decorations  ;  with  a  Practical  Treatise  on  House  Paint- 
ing. By  D.  R.  Hay,  House  Painter  and  Decorator.  Il- 
lustrated by  a  Diagram  of  the  Primary,  Secondary  and 
Tertiary  Colors.  12mo.  (In  press.) 
12 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


Inventor's  Guide — Patent  Office  and  Patent 
Laws: 

Or,  a  Guide  to  Inventors,  and  a  Book  of  Reference  for 
Judges,  Lawyers,  Magistrates,  and  others.  By  J.  Gr. 
Moore.    12mo.,  cloth  $1.00 

Jervis.   Railway  Property,   A  Treatise 

On  the  Construction  and  Management  of  Railways  ;  de- 
signed to  afford  useful  knowledge,  in  the  popular  style, 
to  the  holders  of  this  class  of  property  ;  as  well  as  Rail- 
way Managers,  Officers  and  Agents.  By  John  B.  Jervis, 
late  Chief  Engineer  of  the  Hudson  River  Railroad,  Cro- 
ton  Aqueduct,  etc.    One  volume,  12mo.,  cloth  $1.50 

CONTENTS.  —  Preface  —  Introduction.  Construction.  —  Introduc- 
tory— Land  and  Land  Damages — Location  of  Line — Method  of  Business 
— Grading — Bridges  and  Culverts— Road  Crossings — Ballasting  Track — 
Cross  Sleepers— Chairs  and  Spikes— Rails— Station  Buildings — Loco- 
motives, Coaches  and  Cars.  Operating. — Introductory — Freight — Pas- 
sengers—Engine Drivers — Repairs  to  Track — Repairs  of  Machinery- 
Civil  Engineer — Superintendent — Supplies  of  Material — Receipts — Dis- 
bursements —  Statistics  —  Running  Trains  —  Competition  —  Financial 
Management — General  Remarks. 

Johnson.  The  Coal  Trade  of  British  America ; 

With  Researches  on  the  Characters  and  Practical  Values 
of  American  and  Foreign  Coals.  By  Walter  R.  Johnson, 
Civil  and  Mining  Engineer  and  Chemist.    8vo  $2.00 

This  volume  contains  the  results  of  the  experiments  made  for  the 
Navy  Department,  upon  which  their  Coal  contracts  are  now  based. 

Johnston.   Instructions  for  the  Analysis  of 
Soils,  Limestones  and  Manures. 

By  J.  F.  W.  Johnston.    12mo  !   38 

Larkin.  The  Practical  Brass  and  Iron  Found- 
er's Guide; 

A  Concise  Treatise  on  the  Art  of  Brass  Founding,  Mould- 
ing, etc.    By  James  Larkin.    12mo.,  cloth  $1.00 

Leslie's  (Miss)  Complete  Cookery; 

Directions  for  (Sookery  in  its  Various  Branches.  By  Miss 
Leslie.  58th  thousand.  Thoroughly  revised  ;  with  the 
addition  of  New  Receipts.    In  one  volume,  12mo.,  half 

hound,  or  in  sheep  $1.00 

13 


PRACTICAL  AND  SCIENTIFIC  BOOKS, 


Leslie's  (Miss)  Ladies'  House  Book; 

A  Manual  of  Domestic  Economy.  20th  revised  edition. 
12mo.,  sheep  $1.00 

Leslie's  (Miss)  Two  Hundred  Receipts  in 
French  Cookery. 

Cloth,  12mo   25 

Lieber.   Assayer's  Guide; 

Or,  Practical  Directions  to  Assayers",  Miners  and  Smelters, 
for  the  Tests  and  Assays,  by  Heat  and  by  Wet  Processes, 
of  the  Ores  of  all  the  principal  Metals,  and  of  Gold  and 
Silver  Coins  and  Alloys.  By  Oscar  M.  Lieber,  late  Geolo- 
gist to  the  State  of  Mississippi.  12mo.  With  illustra- 
tions   75 

"  Among  the  indispensable  works  for  this  purpose,  is  this  little 
guide."— Artizan. 

Lowig.   Principles  of  Organic  and  Physiologi- 
cal Chemistry, 

By  Dr.  Carl  Lowig,  Doctor  of  Medicine  and  Philosophy; 
Ordinary  Professor  of  Chemistry  in  the  University  of 
Zurich  ;  Author  of  M  Chemie  des  Organischen  Verbindun 
gen."  Translated  by  Daniel  Breed,  M.  D.,  of  the  U.  S. 
Patent  Office  ;  late  of  the  Laboratory  of  Liebig  and  Lowig. 
8vo.,  sheep  $3.50 

Marble  Worker's  Manual; 

Containing  Practical  Information  respecting  Marbles  in 
general,  their  Cutting,  Working  and  Polishing,  Veneer- 
ing, etc.,  etc.    12mo.,  cloth  $1.00 

Miles,   A  Plain  Treatise  on  Horseshoeing, 

With  Illustrations.  By  William  Miles,  Author  of  "The 
Horse's  Foot."   75 

Morfit.   The  Arts  of  Tanning,  Currying  and 
Leather  Dressing, 

Theoretically  and  Practically  Considered  in  all  their  De- 
tails ;  being  a  Full  and  Comprehensive  Treatise  on  the 
14 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


Manufacture  of  the  Various  Kinds  of  Leather.  Illus- 
trated by  over  two  hundred  Engravings.  Edited  from  the 
French  of  De  Fontenelle  and  Malapeyere.  With  nu- 
merous Emendations  and  Additions,  by  Campbell  Morfit, 
Practical  and  Analytical  Chemist.  Complete  in  one  vol- 
ume, octavo  $10.00 

This  important  Treatise  will  be  found  to  cover  the  whole  field  in 
the  most  masterly  manner,  and  it  is  believed  that  in  no  other  branch 
of  applied  science  could  more  signal  service  be  rendered  to  American 
Manufactures. 

The  publisher  is  not  aware  that  in  any  other  work  heretofore  issued 
in  this  country,  more  space  has  been  devoted  to  this  subject  than  a  "' 
single  chapter  ;  and  in  offering  this  volume  to  so  large  and  intelligent 
a  class  as  American  Tanners  and  Leather  Dressers,  he  feels  confident 
of  their  substantial  support  and  encouragement.  » 

CONTENTS.— Introduction— Dignity  of  Labor— Tan  and  Tannin 
— Gallic  Acid — Extractive-Tanning  Materials — Oak  Barks — Barking 
of  Trees — Method  of  Estimating  the  Tanning  Power  of  Astringent 
Substances — Tan— The  Structure  and  Composition  of  Skin — Different 
Kinds  of  Skin  suitable  for  Tanning — Preliminary  Treatment  of  Skins 
— Tanning  Process — Improved  Processes — Vauquelin's  Process— Ac- 
celerating Processes — Keasley's,  Trumbull's,  Hibbard's,  and  Leprieur's 
Processes — Tanning  with  Extract  of  Oak-Bark — Hemlock  Tanning — 
With  Myrtle  Plant— English  Harness  Leather— Calf  Skins—  Goat  and 
Sheep  Skins — Horse  Hides— Buck.  Wolf  and  Dog  Skins— Buffalo,  or 
M  Grecian"  Leather — Russia  Leather — Red  Skins — Wallachia  Leather 
— Mineral  Tanning— Texture  and  Quality  of  Leather,  and  the  means 
of  Discovering  its  Defects— Tawing — Hungary  Leather — Oiled  Leather 
— Tanning  as  practised  by  the  Mongol  Tartars— Shagreen — Parchment 
— Leather  Bottles — Tanning  of  Cordage  and  Sail  Cloth— Glazed  or 
11  Patent"  Leather — Helverson's  Process  for  Rendering  Hides  Hard 
and  Transparent — Currying— Currying  of  Calf  Skins— Currying  of 
Goat  Skins — Red  Leather — Fair  Leather— Water  Proof  Dressing — 
Perkins'  Machine  for  Pommelling  and  Graining  Leather — Splitting, 
Shaving,  Fleshing  and  Cleansing  Machines— Embossing  of  Leather- 
Gut  Dressing. 


Morfit.   A  Treatise  on  Chemistry 

Applied  to  the  Manufacture  of  Soap  and  Candles  ;  being 
a  Thorough  Exposition,  in  all  their  Minutiae,  of  the  prin- 
ciples and  Practice  of  the  Trade,  based  upon  the  most 
recent  Discoveries  in  Science  and  Art.  By  Campbell 
Morfit,  Professor  of  Analytical  and  Applied  Chemistry  in 
the  University  of  Maryland.  A  new  and  improved  edi- 
tion. Illustrated  with  260  Engravings  on  Wood.  Com- 
plete in  one  volume,  large  8vo  $6.00 

CONTENTS. — CHAPTER  I.  The  History  of  the  Art  and  its  Rela- 
tions to  Science— II.  Chemical  Combination— III.  Alkalies  and  Alka- 
line Earths — IV.  Alkalimentary — V.  Acids — VI.  Origin  and  Composi- 
tion of  Fatty  Matters — VII.  Saponifiable  Fats — Vegetable  Fats— Ani- 
mal Fats— Waxes — VIII.  Action  of  Heat  and  Mineral  Acids  of  Fatty 
Matters — IX.  Volatile  or  Essential  Oils,  and  Resins — X.  The  Proxi- 
mate Principles  of  Fats — Their  Composition  and  Properties— Basic 
Constituents  of  Fats— XI.  Theory  of  Saponification— XII.  Utensils 
Requisite  for  a  Soap  Factory — XIII.  Preparatory  Manipulations  in 
the  Process  of  Making  Soap— Preparation  of  the  Lyea— XIV.  Hard 


PRACTICAL  ALTD  SCIENTIFIC  BOOKS, 


Soaps— XV.  Soft  Soaps— XVI.  Soaps  by  the  Cold  Process— XVII.  Sili- 
cated  Soaps— XVIII.  Toilet  Soaps— XIX.  Patent  Soaps— XX.  Fraud 
and  Adulterations  in  the  Manufacture  of  Soap— XXI.  Candles— XXII. 
Illumination— XXIII.  Philosophy  of  Flame— XXIV.  Raw  Material 
for  Candles— Purification  and  Bleaching  of  Suet— XXV.  Wicks— XXVI. 
Dipped  Candles— XXVII.  Moulded  Candies— XXVIII.  Stearin  Candles 
— XXIX.  Stearic  Acid  Candles — "Star"  or  "Adamantine"  Candles— 
Saponification  by  Lime — Saponification  by  Lime  and  Sulphurous  Acid 
—Saponification  by  Sulphuric  Acid— Saponification  by  the  combined 
action  of  Heat,  Pressure  and  Steam — XXX.  Spermaceti  Candles — 
XXXI.  Wax  Candles— XXXII.  Composite  Candles— XXXIII.  Paraffin 
—XXXIV.  Patent  Candles— XXXV.  Hydrometers  and  Thermometers. 

M  orthner.   Pyrotechnist' s  Companion ; 

Or,  a  Familiar  System  of  Fire-works.  By  Gr.  W.  Morti- 
mer.   Illustrated  by  numerous  Engravings.    12mo...  75 

Napier.   Manual  of  Electro-Metallurgy; 

Including  the  Application  of  the  Art  to  Manufacturing 
Processes.  By  James  Napier.  From  the  second  London 
edition,  revised  and  enlarged.  Illustrated  by  Engrav- 
ings.   In  one  volume,  12mo  $1.50 

Napier's  Electro-Metallurgy  is  generally  regarded  as  the  very  best 
Practical  Treatise  on  the  Subject  in  the  English  Language. 

CONTENTS.— History  of  the  Art  of  Electro-Metallurgy— Descrip- 
tion of  Galvanic  Batteries,  and  their  respective  Peculiarities— Elec- 
trotype Processes — Miscellaneous  Applications  of  the  Process  of  Coat- 
ing with  Copper — Bronzing — Decomposition  of  Metals  upon  one 
another — Electro-Plating — Electro-Gilding — Results  of  Experiments 
on  the  Deposition  of  other  Metals  as  Coatings,  Theoretical  Observa- 
tions. 

Norris' s  Hand-book  for  Locomotive  Engineers 
and  Machinists ; 

Comprising  the  Calculations  for  Constructing  Locomo- 
tives, Manner  of  setting  Valves,  etc.,  etc.  By  Septimus 
Norris,  Civil  and  Mechanical  Engineer.  In  one  volume, 
12mo.,  with  Illustrations  !  ....$1.50 

"  With  pleasure  do  we  meet  with  such  a  work  as  Messrs.  Norris 
and  Baird  have  given  us."— Artizan. 

u  In  this  work  he  has  given  us  what  are  called  'the  secrets  of  the 
business,'  in  the  rules  to  construct  locomotives,  in  order  that  the  mil- 
lion should  be  learned  in  all  things." — Scientific  American. 

Nystrom.  A  Treatise  on  Screw-Propellers  and 
their  Steam-Engines ; 

With  Practical  Rules  and  Examples  by  which  to  Calcu- 
late and  Construct  the  same  for  any  description  of  Ves- 
sels. By  J.  W.  Nystrom.  Illustrated  by  over  thirty 
large  Working  Drawings.  In  one  volume,  octavo... $3.50 
l(i 


PUBLISHED  BY  HENBY  CABBY  BAIBD. 


Overman.   The  Manufacture  of  Iron  in  all  its 
Various  Branches; 

To  which  is  added  an  Essay  on  the  Manufacture  of  Steel. 
By  Frederick  Overman,  Mining  Engineer.  With  one 
hundred  and  fifty  Wood  Engravings.  Third  edition.  In 
one  volume,  octavo,  five  hundred  pages  $6.00 

"  We  have  now  to  announce  the  appearance  of  another  valuable 
work  on  the  subject,  which,  in  our  humble  opinion,  supplies  any  defi- 
ciency which  late  improvements  and  discoveries  may  have  caused, 
from  the  lapse  of  time  since  the  date  of  '  Mushet'  and  '  Schrivenor.' 
It  is  the  production  of  one  of  our  Trans- Atlantic  brethren,  Mr.  Fred- 
erick Overman,  Mining  Engineer  ;  and  we  do  not  hesitate  to  set  it 
down  as  a  work  of  great  importance  to  all  connected  with  the  iron  in- 
terests ;  one  which,  while  it  is  sufficiently  technological  fully  to  ex- 
plain chemical  analysis,  and  the  various  phenomena  of  iron  under 
different  circumstances,  to  the  satisfaction  of  the  most  fastidious,  is 
written  in  that  clear  and  comprehensive  style  as  to  be  available  to  the 
capacity  of  the  humblest  mind,  and  consequently  will  be  of  much  ad- 
vantage to  those  works  where  the  proprietors  may  see  the  desirability 
of  placing  it  in  the  hands  of  their  operatives."— London  Mining 
Journal, 

Painter,  Gilder  and  Varnisher's  Companion; 

Containing  Rules  and  Regulations  in  everything  relating 
to  the  Arts  of  Painting,  Gilding,  Varnishing  and  Glass 
Staining  ;  with  numerous  useful  and  valuable  Receipts  ; 
Tests  for  the  detection  of  Adulterations  in  Oils  and 
Colors  ;  and  a  statement  of  the  Diseases  and  Accidents  to 
which  Painters,  Gilders  and  Varnishers  are  particularly 
liable,  with  the  simplest  methods  of  Prevention  and 
Remedy.  Eighth  edition.  To  which  are  added  Complete 
Instructions  in  Graining,  Marbling,  Sign  Writing,  and 
Gilding  on  Glass.    12mo.,  cloth   75 

Paper-Hanger's  (The)  Companion; 

In  which  the  Practical  Operations  of  the  Trade  are  sys- 
tematically laid  down  ;  with  copious  Directions  Prepara- 
tory to  Papering  ;  Preventions  against  the  effect  of  Damp 
in  Walls  ;  the  various  Cements  and  Pastes  adapted  to 
the  several  purposes  of  the  Trade  ;  Observations  and  Di- 
rections for  the  Panelling  and  Ornamenting  of  Rooms, 
etc.,  etc.  By  James  Arrowsmith.  In  one  volume, 
12mo   75 

Practical  (The)  Surveyor's  Guide; 

Containing  the  necessary  information  to  make  any  per- 
son of  common  capaeitv  a  finished  Land  Survevor,  with- 

*  17 


PHACTICAL  AND  SCIENTIFIC  BOOKS, 


out  the  aid  of  a  Teacher.  By  Andrew  Duncan,  Land 
Surveyor  and  Civil  Engineer.    12mo   75 

Having  had  an  experience  as  a  Practical  Surveyor,  etc.,  of  thirty 
years,  it  is  believed  that  the  author  of  this  volume  possesses  a  thorough 
knowledge  of  the  wants  of  the  profession  ;  and  never  having  met  with 
any  work  sufficiently  concise  and  instructive  in  the  several  details 
necessary  for  the  proper  qualification  of  the  Surveyor,  it  has  been  his 
object  to  supply  that  want.  Among  other  important  matters  in  the 
book,  will  be  found  the  following  : 

Instructions  in  levelling  and  profiling,  with  a  new  and  speedy  plan 
of  setting  grades  on  rail  and  plank  roads — the  method  of  inflecting 
curves — the  description  and  design  of  a  new  instrument,  whereby  dis- 
tances are  found  at  once,  without  any  calculation — a  new  method  of 
surveying  any  tract  of  land  by  measuring  one  line  through  it — a  geo- 
metrical method  of  correcting  surveys  taken  with  the  compass,  to  fit 
them  for  calculation — a  short  method  of  finding  the  angles  from  the 
courses,  and  vice  versa — the  method  of  surveying  with  the  compass 
through  any  mine  or  iron  works,  and  to  correct  the  deflections  of  the 
needle  by  attraction — description  of  an  instrument  by  the  help  of 
which  any  one  may  measure  a  map  by  inspection,  without  calculation 
— a  new  and  short  method  of  calculation,  wherein  fewer  figures  are 
used — the  method  of  correcting  the  diurnal  variation  of  the  needle 
— various  methods  of  plotting  and  embellishing  maps — the  most  cor- 
rect method  of  laying  off  plots  with  the  pole,  etc. — description  of  a 
new  compass  contrived  by  the  author,  etc.,  etc. 

Railroad  Engineer's  Pocket  Companion  for  the 
Field. 

By  W.  Griswold.    12mo.,  tucks  $1.00 

Riddell,   The  Elements  of  Hand-Railing ; 

Being  the  most  Complete  and  Original  Exposition  of  this 
Branch  of  Carpentry  that  has  appeared.  By  Robert 
Riddell.  Third  edition.  Enlarged  and  improved.  Il- 
lustrated by  22  large  plates.    4to.,  cloth  $3.00 

Rural  Chemistry; 

An  Elementary  Introduction  to  the  Study  of  the  Science, 
in  its  relation  to  Agriculture  and  the  Arts  of  Life.  By 
Edward  Solly,  Professor  of  Chemistry  in  the  Horticul- 
tural Society  of  London.    From  the  third  improved  Lon- 


don edition.    12mo  $1.25 

Sliimk.   A  Practical  Treatise 

On  Railway  Curves,  and  Location  for  Young  Engineers. 
By  Wm.  F.  Shunk,  Civil  Engineer.    12mo  $1.00 


Strength  and  Other  Properties  of  Metals; 

Reports  of  Experiments  on  the  Strength  and  other  Pro 
18 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


perties  of  Metals  for  Cannon.  With  a  Description  of  the 
Machines  for  Testing  Metals,  and  of  the  Classification  of 
Cannon  in  service.  By  Officers  of  the  Ordnance  Depart- 
ment U.  S.  Army.  By  authority  of  the  Secretary  of 
War.  Illustrated  by  25  large  steel  plates.  In  one  vol- 
ume, quarto  .....$10.00 

The  best  Treatise  on  Cast-iron  extant. 

Tables  Showing  the  Weight 

Op  Rounp,  Square  and  Flat  Bar  Iron,  Steel,  etc.,  by 
Measurement.     Cloth   50 

Taylor.   Statistics  of  Coal; 

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duction and  Consumption  on  the  American  Continent. 
With  Incidental  Statistics  of  the  Iron  Manufacture.  By 
R.  C.  Taylor.  Second  edition,  revised  by  S.  S.  Halde- 
man.  Illustrated  by  five  Maps  and  many  Wood  Engrav- 
ings.   8vo.,  cloth  $6.00 

Templeton,    The  Practical  Examinator  on 
Steam  and  the  Steam  Engine ; 

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it  would  be  equally  useful  to  them  as  it  had  been  to  himself. 

Tin  and  Sheet  Iron  Worker's  Instructor; 

Comprising  complete  Descriptions  of  the  necessary  Pat- 
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Treatise  (A)  on  a  Box  of  Instruments, 

And  the  Slide  Rule  ;  with  the  Theory  of  Trigonometry 
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ing,  Measuring  of  Timber,  Cask  and   Malt  Gauging, 

19 


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ning. Together  with  an  Appendix  containing  several 
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Turnbull,  M.  D.,  Lecturer  on  Technical  Chemistry  at  the 
Franklin  Institute.  Second  edition.  Revised  and  im- 
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Turner's  (The)  Companion; 

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SOCIAL  SCIENCE. 

THE  WORKS  OP  HENRY  C.  CAREY. 


"  I  challenge  the  production  from  among  the  writers  on  political 
economy  of  a  more  learned,  philosophical,  and  convincing  speculator 
on  that  theme,  than  my  distinguished  fellow-citizen,  Henry  C.  Carey. 
The  works  he  has  published  in  support  of  the  protective  policy,  are 
remarkable  for  profound  research,  extensive  range  of  inquiry,  rare 
logical  acumen,  and  a  consummate  knowledge  of  history." — Speech  of 
Hon.  Edward  Joy  Morris,  in  the  House  of  Representatives  of  the  United 
States,  February  2,  1869. 

20 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


THE  WORKS  OF  HENRY  C.  CAREY. 


"  Henry  C.  Carey,  the  best  known  and  ablest  economist  of  North 
America.  *****  in  Europe  he  is  principally  known  by  his 
striking  and  original  attacks,  based  upon  the  peculiar  advantages  of 
American  experience,  on  some  of  the  principal  doctrines,  especially 
Malthas'  '  Theory  of  Population'  and  Ricardo's  teachings.  His  views 
have  been  largely  adopted  and  thoroughly  discussed  in  Europe." — 
"  The  German  Political  Lexicon,"  Edited  by  Bluntschli  and  Brater.  Leipsic, 
1858. 

"  We  believe  that  your  labors  mark  an  era  in  the  science  of  political 
economy.  To  your  researches  and  lucid  arguments  are  we  indebted 
for  the  explosion  of  the  absurdities  of  Malthus,  Say,  and  Ricardo,  in 
regard  to  the  inability  of  the  earth  to  meet  the  demands  of  a  growing 
population.  American  industry  owes  you  a  debt  which  cannot  be  re- 
paid, and  which  it  will  ever  be  proud  to  acknowledge. — From  a  Letter 
of  Hon.  George  W.  Scranton,  M.  u.,  Hon.  William  Jessup,  and  over  sixty 
influential  citizens  of  Luzerne  County,  Pennsylvania,  to  Henry  C.  Carey, 
April  3,  1859. 


Financial  Crises; 

Their  Causes  and  Effects.    8vo.,  paper   25 

French  and  American  Tariffs, 

Compared  in  a  Series  of  Letters  addressed  to  Mons.  M. 
Chevalier.    8vo.,  paper   15 

Harmony  (The)  of  Interests; 

Agricultural,  Manufacturing  and  Commercial.  8vo., 

paper   75 

Cloth  $1.25 


u  We  can  safely  recommend  this  remarkable  work  to  all  who  wish 
to  investigate  the  causes  of  the  progress  or  decline  of  industrial  com- 
munities."— Blackwood's  Magazine. 

Letters  to  the  President  of  the  United  Slates. 

8vo.,  Paper   50 

Miscellaneous  Works; 

Comprising  "  Harmony  of  Interests,"  "  Money,"  "Let- 
ters to  the  President,"  "French  and  American  Tariffs," 
and  "  Financial  Crises."    One  volume,  8vo.,  half  bound. 

$2.25 

Money;  A  Lecture 

Before  the  New  York  Geographical  and  Statistical  So- 
ciety.   8vo.,  paper   15 

21 


PBACTICAIi  AND  SCIENTIFIC  BOOKS, 


THE  WORKS  OF  HENRY  C.  CAREY. 


Past  (The),  the  Present,  and  the  Future, 

8vo  $2.00 

12mo  $1.25 

"  Full  of  important  facts  bearing  on  topics  that  are  now  agitating 
all  Europe.  *  *  *  These  quotations  will  only  whet  the  appetite 
of  the  scientific  reader  to  devour  the  whole  work.  It  is  a  book  full  of 
valuable  information." — Economist. 

"  Decidedly  a  book  to  be  read  by  all  who  take  an  interest  in  the  pro- 
gress of  social  science." — Spectator. 

"A  Southern  man  myself,  never  given  to  tariff  doctrines,  I  confess  to 
have  been  convinced  by  his  reasoning,  and,  thank  Heaven,  have  not 
now  to  learn  the  difference  between  dogged  obstinacy  and  consistency. 
4  Ye  gods,  give  us  but  light !'  should  be  the  motto  of  every  inquirer 
after  truth,  but  for  far  different  and  better  purposes  than  that  which 
prompted  the  exclamation." — The  late  John  S.  Skinner. 

"  A  volume  of  extensive  information,  deep  thought,  high  intelli- 
gence, and  moreover  of  material  utility." — London  Morning  Advertiser. 

"  Emanating  from  an  active  intellect,  remarkable  for  distinct  views 
and  sincere  convictions." — Britannia. 

"  4  The  Past,  Present,  and  Future,'  is  a  vast  summary  of  progressive 
philosophy,  wherein  he  demonstrates  the  benefit  of  political  economy 
in  the  onward  progress  of  mankind,  which,  ruled  and  directed  by  over- 
whelming influences  of  an  exterior  nature,  advances  little  by  little, 
until  these  exterior  influences  are  rendered  subservient  in  their  turn, 
to  increase  as  much  as  possible  the  extent  of  their  wealth  and  riches." 
— Diciionnaire  Universel  des  Contemporains,  Par  G.  Vapereau,  Paris^ 
1858. 

Principles  of  Social  Science, 

Three  volumes,  8vo.,  cloth  $7.50 

CONTENTS.— Volume  I.  Of  Science  and  its  Methods— Of  Man, 
the  Subject  of  Social  Science— Of  Increase  in  the  Numbers  of  Mankind 
—Of  the  Occupation  of  the  Earth— Of  Value— Of  Wealth— Of  the  For- 
mation of  Society — Of  Appropriation — Of  Changes  of  Matter  in  Place 
— Of  M  hanical  and  Chemical  Changes  in  the  Forms  of  Matter.  Vol- 
ume II.  Of  Vital  Changes  in  the  Form  of  Matter — Of  the  Instrument 
of  Association.  Volume  III.  Of  Production  and  Consumption — Of 
Accumulation — Of  Circulation — Of  Distribution — Of  Concentration 
and  Centralization— Of  Competition — Of  Population — Of  Food  and 
Population— Of  Colonization — Of  the  Malthusian  Theory— Of  Com- 
merce—Of  the  Societary  Organization — Of  Social  Science. 

"  I  have  no  desire  here  to  reproach  Mr.  Malthus  with  the  extreme 
lightness  of  his  scientific  baggage.  In  his  day,  biology,  animal  and 
vegetable  chemistry,  the  relations  of  the  various  portions  of  the  hu- 
man organism,  etc.  etc.,  had  made  but  little  progress,  and  it  is  to  the 
general  ignorance  in  reference  to  these  questions  that  we  must,  as  I 
think,  look  for  explanation  of  the  fact  that  he  should,  with  so  much 
confidence,  in  reference  to  so  very  grave  a  subject,  have  ventured  to 
suggest  a  formula  so  arbitrary  in  its  character,  and  one  whose  hollow- 
ness  becomes  now  so  clearly  manifest.  Mr.  Carey's  advantage  over 
him,  both  as  to  facts  and  logic,  is  certainly  due  in  great  part  to  the 

f>rogress  that  has  since  been  made  in  all  the  sciences  connected  with 
ife  ;  but  then,  how  admirably  has  he  profited  of  them  !  How  entirely 
is  he  au  courant  of  all  these  branches  of  knowledge  which,  whether 
22 


PUBLISHED  BY  HENRY  CAREY  BAIRD. 


THE  WORKS  OF  HENRY  C.  CAREY. 


directly  or  indirectly,  bear  upon  his  subject !  With  what  skill  does  he 
ask  of  each  and  every  of  them  all  that  it  can  be  made  to  furnish, 
■whether  of  facts  or  arguments  !  With  what  elevated  views,  ana 
what  amplitude  of  means,  does  he  go  forward  in  his  work  !  Above 
all,  how  thorough  in  his  scientific  caution  !  Accumulating  inductions, 
and  presenting  for  consideration  facts  the  most  undoubted  and  proba- 
bilities of  the  highest  kind,  he  yet  affirms  nothing,  contenting  himself 
with  showing  that  his  opponent  had  no  good  reason  for  affirming  the 
nature  of  the  progression,  nor  the  time  of  duplication,  nor  the  gene- 
ralization which  takes  the  facts  of  an  individual  case  and  deduces 
from  them  a  law  for  every  race,  every  climate,  every  civilization, 
every  condition,  moral  or  physical,  permanent  and  transient, 
healthy  or  unhealthy,  of  the  various  populations  of  the  many  coun- 
tries of  the  world.  Then,  having  reduced  the  theory  to  the  level  of  a 
mere  hypothesis,  he  crushes  it  to  atoms  under  the  weight  of  facts." — 
M.  De  Fontenay  in  the  "Journal  des  Economistes."   Paris,  September,  1862. 

"  This  book  is  so  abundantly  full  of  notices,  facts,  comparisons,  cal- 
culations, and  arguments,  that  too  much  would  be  lost  by  laying  a 
part  of  it  before  the  eye  of  the  reader.  The  work  is  vast  and  severe 
in  its  conception  and  aim,  and  is  far  removed  from  the  common  run 
of  the  books  on  similar  subjects." — 11  Mondo  Letterario,  Turin. 

"  In  political  economy,  America  is  represented  by  one  of  the 
strongest  and  most  original  writers  of  the  age,  Henry  C.  Carey,  of 
Philadelphia.  *********** 

"  His  theory  of  Rents  is  regarded  as  a  complete  demonstration  that 
the  popular  views  derived  from  Ricardo  are  erroneous  ;  and  on  the 
subject  of  Protection,  he  is  generally  confessed  to  be  the  master- 
thinker  of  his  country." — Westminster  Review. 

"  Both  in  America  and  on  the  Continent,  Mr.  Henry  Carey  has  ac- 
quired a  great  name  as  a  political  economist.  ***** 

"  His  refutation  of  Malthus  and  Ricardo  we  consider  most  triumph- 
ant."— London  Critic. 

"  Mr.  Carey  began  his  publication  of  Principles  twenty  years  ago  ; 
he  is  certainly  a  mature  and  deliberate  writer.  More  than  this,  he  is 
readable  :  his  pages  swarm  with  illustrative  facts  and  with  American 
instances.  ************ 

"  We  are  in  great  charity  with  books  which,  like  Mr.  Carey's,  theo- 
rize with  excessive  boldness,  when  the  author,  as  does  Mr.  Carey, 
possesses  information  and  reasoning  power."— London  Athenceum. 

"  Those  who  would  fight  against  the  insatiate  greed  and  unscrupu- 
lous misrepresentations  of  the  Manchester  school,  which  we  have  fre- 
quently exposed,  without  any  of  their  organs  having  ever  dared  to 
make  reply,  will  find  in  this  and  Mr.  Carey's  other  works  an  immense 
store  of  arms  and  ammunition.  ******** 

li  An  author  who  has,  among  the  political  economists  of  Germany 
and  France,  numerous  readers,  is  worth  attentive  perusal  in  Eng- 
land."— London  Statesman. 

"  Of  all  the  varied  answers  to  the  old  cry  of  human  nature, 4  Who 
will  show  us  any  good  V  none  are  more  sententious  than  Mr.  Carey's. 
He  says  to  Kings,  Presidents,  and  People,  '  Keep  the  nation  at  work, 
and  the  greater  the  variety  of  employments  the  better.'  He  is  seek- 
ing and  elucidating  the  great  radical  laws  of  matter  as  regards  man. 
He  is  at  once  the  apostle  and  evangelist  of  temporal  righteousness." 
— National  Intelligencer. 

"  A  work  which  we  believe  to  be  the  greatest  ever  written  by  an 
American,  and  one  which  will  in  future  ages  be  pointed  out  as  the 
most  successful  effort  of  its  time  to  form  the  great  scientia  scientiarum.^ 
—Philadelphia  Evening  Bulletin. 

23 


PRACTICAL  AND  SCIENTIFIC  BOOKS, 


THE  WORKS  OF  HENRY  C.  CAREY. 


The  Slave  Trade,  Domestic  and  Foreign; 

Why  it  Exists,  and  How  it  may  be  Extinguished.  12rao., 
cloth  ,  $1.25 

CONTENTS —The  Wide  Extent  of  Slavery— Of  Slavery  in  the 
British  Colonies — Of  Slavery  in  the  United  States — Of  Emancipation 
in  the  British  Colonies— How  Man  passes  from  Poverty  and  Slavery 
toward  Wealth  and  Freedom — How  Wealth  tends  to  Increase — How 
Labor  acquires  Value  and  Man  becomes  Free — How  Man  passes  from 
Wealth  and  Freedom  toward  Poverty  and  Slavery — How  Slavery 
grew,  and  How  it  is  now  maintained  in  the  West  Indies— How  Slavery 
grew,  and  is  maintained  in  the  United  States — How  Slavery  grows  in 
Portugal  and  Turkey — How  Slavery  grows  in  India — How  Slavery 
grows  in  Ireland  and  Scotland— How  Slavery  grows  in  England — 
How  can  Slavery  be  extinguished]— How  Freedom  grows  in  Northern 
Germany — How  Freedom  grows  in  Russia — How  Freedom  grows  in 
Denmark — How  Freedom  grows  in  Spain  and  Belgium — Of  the  Duty 
of  the  People  of  the  United  States— Of  the  Duty  of  the  People  of  Eng- 
land. 

"  As  a  philosophical  writer,  Mr.  Carey  is  remarkable  for  the  union 
of  comprehensive  generalizations  with  a  copious  induction  of  facts. 
His  research  of  principles  never  leads  him  to  the  neglect  of  details  ; 
nor  is  his  accumulation  of  instances  ever  at  the  expense  of  universal 
truth.  He  is,  doubtless,  intent  on  the  investigation  of  laws,  as  the 
appropriate  aim  of  science,  but  no  passion  for  theory  seduces  him 
into  the  region  of  pure  speculation.  His  mind  is  no  less  historical 
than  philosophical,  and  had  he  not  chosen  the  severer  branch  in 
which  his  studies  have  borne  such  excellent  fruit,  he  would  have 
attained  an  eminent  rank  among  the  historians  from  whom  the  litera- 
ture of  our  country  has  received  such  signal  illustration." — New  York 
Tribune, 


French  Politico-Economic  Controversy, 

Between  the  Supporters  of  the  Doctrines  of  Carey  and 
of  those  of  Ricardo  and  Malthus.  By  MM.  De  Fontenay, 
Dupuit,  Baudrillart,  and  others.  Translated  from  the 
"  Journal  des  Economistes,"  1862-63.    (In  press.) 

Protection  of  Home  Labor  and  Home  Produc- 
tions 

Necessary  to  the  Prosperity  of  the  American  Farmer. 
By  H.  C.  Baird.    Paper   13 

Smith,   A  Manual  of  Political  Economy. 

By  E.  Peshine  Smith.    12mo.,  cloth.   $1.25 


24 


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GETTY  CENTER  LIBRARY 


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